^ DESCRIPTION
THERMOELECTRIC CONVERTER ELEMENT,
METHOD OF MANUFACTURING THERMOELECTRIC CONVERTER ELEMENT, AND
5 THERMOELECTRIC CONVERSION METHOD
Technical Field:
The present invention relates to a thermoelectric converter element using a magnetic
material, a method of manufacturing a thermoelectric converter element, and a thermoelectric
10 conversion method.
Background of the Invention:
In recent years, efforts have actively been made toward environmental issues and energy
issues for the sustainable society. Expectations of thermoelectric converter elements have
15 grown under such circumstances.
This is because heat is the most common energy source that is available from various
media, such as body temperature, sunlight, engines, and industrial exhaust heat.
Therefore, thermoelectric converter elements are expected to become more important in
future for efficiency enhancement in energy use for a low-carbon economy or for applications of
20 power supply to ubiquitous terminals, sensors, or the like.
Heretofore, a bulk thermoelectric converter element comprising a thermocouple module
structure assembled by processing and bonding a sintered compact of a thermoelectric
i semiconductor such as Bi2Te3 has commonly been used as a structure of a thermoelectric
converter element. However, a thin-film thermoelectric element comprising a module produced
25 by depositing a thin film of a thermoelectric semiconductor on a substrate by a sputtering method
or the like has progressed in development and attracted attention.
Examples of the advantages of such a thin-film thermoelectric converter element are
given as follows: (1) A thin-film thermoelectric converter is small in size and light in weight.
(2) A collective deposition for a large area can be achieved by sputtering, coating, printing, or the
30 like. Thus, the productivity is high. (3) Cost can be reduced by using an inexpensive
substrate. (4) A flexible thermoelectric converter element can be obtained by using a highly
flexible substrate.
Here, thin-film thermoelectric converter elements have heretofore been produced by
coating or printing. For example, according to Patent Literature 1, powdered Bi2Te3 is mixed
2
vjfla a binder into paste, which is applied onto a substrate by a screen printing method or the like
so as to form a thermoelectric element pattern. Furthermore, according to Patent Literature 2,
an ink including a thermoelectric semiconductor material and an electrode material is
pattern-printed by an ink jet method so as to form a thermoelectric element. Moreover,
5 according to Patent Literature 3, an organic semiconductor is used as a thermoelectric material,
and a thermoelectric element is formed by a printing process.
However, there has been a problem that the aforementioned thin-film thermoelectric
element is so thin that it has difficulty in generating and holding a temperature difference
between a front face and a rear face of the thin film. Specifically, in most of power generation
10 applications, a temperature difference (temperature gradient) is imparted in a direction
perpendicular to a thin-film surface comprising a thermoelectric material, so that thermoelectric
conversion is performed. As the film thickness of a thin film of a thermoelectric semiconductor
is reduced, thermal insulation (thermal resistance) becomes insufficient. Therefore, it becomes
difficult to maintain a temperature difference between a front face and a rear face of the thin film
15 of the thermoelectric semiconductor. Alternatively, a temperature difference is mostly
generated between a front face and a rear face of a substrate, rather than a front face and a rear
face of the thin film of the thermoelectric semiconductor. Accordingly, efficient power
generation cannot be achieved.
In order to improve the thermal insulation property, one of the following two solutions
20 may be taken: (1) The film thickness of a thermoelectric semiconductor film is increased (for
example, to at least several times 10 urn). (2) The thermal conductivity of a thermoelectric
semiconductor is reduced.
However, in the case of the solution (1), it becomes difficult to pattern and produce a
thermocouple structure by a coating process, a printing process, or the like if the film thickness
25 of a thermoelectric semiconductor film increases. Therefore, the productivity decreases. Thus,
a trade-off arises between increased conversion efficiency and reduced cost productivity.
Furthermore, in the case of the solution (2), a material having a lower thermal
conductivity tends to have a lower electric conductivity. Additionally, a thermoelectric material
having a high electric conductivity is required for conventional thermoelectric generation. In
30 view of those facts, a trade-off still arises between the electric conductivity and the thermal
conductivity. Therefore, there is a limit in reduction of the thermal conductivity.
Meanwhile, in recent years, there has been discovered the spin Seebeck effect, which
generates electron spin currents when a temperature gradient is applied to a magnetic material.
Patent Literature 4 and Non-Patent Literatures 1 and 2 disclose a thermoelectric
3
cjfi^erter element based upon the spin Seebeck effect and illustrate a structure in which currents
of angular momentum (spin currents) caused by the spin Seebeck effect are derived as an electric
current (electromotive force) by the inverse spin Hall effect.
For example, a thermoelectric converter element disclosed in Patent Literature 4
5 includes a ferromagnetic metal film deposited by a sputtering method and a metal electrode.
With this configuration, when a temperature gradient is applied in a direction parallel to a surface
of the ferromagnetic metal film, spin currents are induced along the temperature gradient by the
spin Seebeck effect. The induced spin currents can be derived as an electric current to the
exterior of the thermoelectric converter element by the inverse spin Hall effect of the metal
10 electrode that is brought into contact with the ferromagnetic metal. Thus, a temperature
difference power generation that derives electric power from heat can be achieved.
Furthermore, a thermoelectric converter element disclosed in Non-Patent Literatures 1
and 2 is formed of a magnetic insulator and a metal electrode.
Specifically, in Non-Patent Literature 1, there has been reported a thermoelectric
15 conversion in which a temperature gradient is arranged in parallel to a surface of the magnetic
insulator (in-plane temperature gradient) as with Patent Literature 4.
Moreover, Non-Patent Literature 2 exemplifies thermoelectric conversion with an
arrangement of a temperature gradient perpendicular to a plate surface of the magnetic insulator
having a thickness of 1 mm (perpendicular-plane temperature gradient).
20 With use of the spin Seebeck effect, a complicated thermocouple structure is not
required, unlike a conventional thermoelectric converter element using a thermocouple module
configuration. Therefore, the aforementioned problems relating to the arrangement patterning
may be solved, and a thin-film thermoelectric converter element that can readily increase its area
at a low cost may be obtained.
25 Furthermore, in a thermoelectric converter element using the spin Seebeck effect, an
electrically conductive portion (electrode) and a thermally conductive portion (magnetic
material) can be designed independently of each other. In theory, a structure having a high
electric conductivity (low ohmic loss) and a low thermal conductivity (capable of holding a
temperature difference between a front face and a rear face thereof) can be implemented.
30 For example, when an insulation material is used for a magnetic material as in
Non-Patent Literatures 1 and 2, heat conduction through electrons can completely be inhibited.
Therefore, development of a high-performance thermoelectric converter element that can achieve
sufficient thermal insulation with a thin-film material is anticipated.
Patent Literature 5 discloses the following structure. Two metal electrodes are
4
P r i d e d on a magnetic and dielectric layer. Spin currents induced in one of the electrodes by
signal currents are exchanged with spins in the magnetic and dielectric layer to generate spin
currents of spin waves and propagate them through the magnetic and dielectric layer. The spin
currents of spin waves and pure spin waves are exchanged with each other at an interface
5 between the other electrode and the magnetic and dielectric layer to thereby generate signal
power on the other electrode. Thus, signal currents are transmitted between the two electrodes
(Patent Literature 5).
Prior Art Literatures:
10 Patent Literature(s)
Patent Literature 1: JP-B 4457705
Patent Literature 2: JP-A 2010-40998
Patent Literature 3: JP-A 2010-199276
Patent Literature 4: JP-A 2009-130070
15 Patent Literature 5: JP-A 2009-295824
Non-Patent Literature(s)
Non-Patent Literature 1: Uchida et al., "Spin Seebeck insulator," Nature Materials, 2010,
vol. 9, p. 894.
Non-Patent Literature 2: Uchida et al., "Observation of longitudinal spin-Seebeck effect
20 in magnetic insulators," Applied Physics Letters, 2010, vol. 97, p. 172505.
Summary of the Invention:
Problem(s) to be Solved by the Invention
The structure of a thermoelectric converter element using the spin Seebeck effect as
25 disclosed in Patent Literature 4 and Non-Patent Literatures 1 and 2 is advantageous in that it can
readily increase its area at a low cost and can achieve thin-film thermoelectric conversion.
Meanwhile, a conventional thermoelectric converter element using the spin Seebeck
effect employs a ferromagnetic metal for a magnetic material serving as a heat conduction
portion in Patent Literature 4 or employs monocrystalline garnet (magnetic insulator) in
30 Non-Patent Literatures 1 and 2.
However, it is difficult to obtain a low thermal conductivity in the case of a metal in
which conduction electrons carry heat or in the case of a monocrystalline insulator having good
crystallinity and demonstrating good phonon conduction. Therefore, it is difficult to hold a
temperature difference between a front face and a rear face of the element. Thus, there is still
5
rtim for improvement in enhancing the performance of thermoelectric conversion.
For example, when a monocrystalline thin film as disclosed in Non-Patent Literature 1
is used, an arrangement of a temperature gradient perpendicular to a surface of the thin film
(perpendicular-plane temperature gradient) cannot achieve sufficient thermal insulation.
5 Therefore, it has been difficult to put highly-efficient thermoelectric power generation into
practice. Additionally, film deposition by liquid phase epitaxial growth (LPE), laser ablation
(PLD), or the like is needed to obtain monocrystal. Therefore, there is room for improvement
in consideration of applications of element production processes that achieves high productivity
at a low cost, such as deposition on a flexible substrate with a large area, high-speed thickness
10 increase, and high-speed multilayering.
Furthermore, use of a bulk magnetic material in the form of a thick plate as in
Non-Patent Literature 2 enables practical thermoelectric power generation with a
perpendicular-plane temperature gradient. However, because of lowered productivity of
production processes or increased material cost, there is still room for improvement to achieve a
15 low-cost and large area element.
Meanwhile, the structure of Patent Literature 5 does not relate to a thermoelectric
converter element. Therefore, as a matter of course, Patent Literature 5 fails to disclose any
problems or solutions on the cost, productivity, and enhancement of the performance of a
thermoelectric converter element.
20 The present invention has been made in view of the above drawbacks. It is, therefore,
an object of the present invention to provide a low-cost thermoelectric converter element having
high productivity and excellent conversion efficiency.
Means for Solving the Problem(s)
In order to achieve the aforementioned object, according to a first aspect of the present
25 invention, a thermoelectric converter element is characterized by comprising a substrate, a
magnetic film provided on the substrate with a certain magnetization direction and formed of a
polycrystalline magnetically insulating material, and an electrode provided on the magnetic film
with a material exhibiting a spin-orbit interaction.
According to a second aspect of the present invention, a method of manufacturing a
30 thermoelectric converter element is characterized by applying a solution containing a magnetic
material on a substrate, heating the substrate to sinter the magnetic material, and depositing an
electrode on the magnetic material so as to produce the thermoelectric converter element as
recited in the first aspect.
According to a third aspect of the present invention, a method of manufacturing a
6
t^Kiioelectric converter element is characterized by blowing particles containing a magnetic
material onto a substrate by an aerosol deposition method to form a magnetic film and depositing
an electrode on the magnetic film so as to produce the thermoelectric converter element as
recited in the first aspect.
5 According to a fourth aspect of the present invention, a thermoelectric conversion
method is characterized by applying a temperature gradient to the magnetic film of the
thermoelectric converter element as recited in the first aspect to generate a spin current flowing
from the magnetic film toward the electrode and generating a current in a direction perpendicular
to the magnetization direction of the magnetic film by an inverse spin Hall effect in the
10 electrode.
According to a fifth aspect of the present invention, a thermoelectric conversion method
is characterized by applying a temperature difference while using, for a low-temperature side, a
side of the substrate of the thermoelectric converter element as recited in the first aspect on
which the magnetic film is provided and using another side of the substrate for a
15 high-temperature side.
Advantageous Effects of the Invention
According to the present invention, there can be provided a low-cost thermoelectric
converter element having high productivity and excellent conversion efficiency.
20 Brief Description of Drawings:
Fig. 1 is a perspective view showing a thermoelectric converter element 1.
Fig. 2 is a cross-sectional view of the thermoelectric converter element 1.
Fig. 3 is a specific example of calculation of the dependency of a lattice-magnon
temperature difference ATmp in the thermoelectric converter element 1 upon a magnetic material
25 film thickness / in a case where a magnon diffusion length X = 10 um, a substrate thickness D = 1
mm, a temperature difference between an upper surface and a lower surface of the element AT =
10 K, and a thermal conductivity Ksub of the substrate 4 was equal to a thermal conductivity Kf,im
of the magnetic film 2 (Kf,im = Ksub).
Fig. 4 is a specific example of calculation of the dependency of ATmp upon the magnetic
30 material film thickness in a case where the magnon diffusion length X = 50 jam in Fig. 3.
Fig. 5 is a graph showing the dependency of the lattice-magnon temperature difference
ATmp in the thermoelectric converter element 1 upon the substrate thickness D in a case where
the thermal conductivity KSUI, of the substrate 4 was equal to the thermal conductivity Kf,im of the
magnetic film 2 (Kfiim = Ksub).
7
Jfc Fig. 6 is a graph showing the dependency of the lattice-magnon temperature difference
ATmp in the thermoelectric converter element 1 upon a ratio "/tW^/m" of the thermal
conductivity of the substrate 4 to the thermal conductivity of the magnetic film 2.
Fig. 7 is a perspective view showing a thermoelectric converter element la.
5 Fig. 8 is a perspective view showing a thermoelectric converter element lb.
Fig. 9 is a diagram modeling a perspective view of a sample of Example 1 and a TEM
(transmission electron microscope) image of a cross-section of the sample.
Fig. 10 is a graph showing the relationship between the magnetic field and the
thermoelectromotive force in the sample of Example 1, illustrating a case where temperature
10 differences (temperature gradients) AT = 1 K, 2 K, and 3 K were applied to an upper surface and
a lower surface of the thermoelectric converter element 1 and a case where no temperature
difference was applied to the upper and lower surfaces of the thermoelectric converter element 1
(AT=0K).
Fig. 11 is a graph showing the relationship between the temperature difference AT and
15 the thermoelectromotive force in the sample of Example 1.
Fig. 12 is a graph showing the dependency of the thermoelectromotive force upon the
film thickness in a case where the film thickness of the sample of Example 1 was varied by
. changing a revolving speed of the magnetic material at the time of spin-coat deposition.
Fig. 13 is a graph showing the relationship between the external magnetic field and the
20 thermoelectromotive force of samples produced by single, double, and triple overlay coatings of
a MOD solution (metal organic decomposition solution) on the sample of Example 1, in which
"step" represents the number of overlay coatings conducted.
Fig. 14 is a graph showing the relationship between the film thickness and the
thermoelectromotive force of samples produced by single, double, and triple overlay coatings of
25 a MOD solution (metal organic decomposition solution) on the sample of Example 1.
Fig. 15 is a schematic view of a thermoelectric converter element using a magnetic film
2 in which YIG (YsFesO^) is doped with a different amount of an impurity of bismuth (Bi) (Bi
is substituted for the Y sites).
Fig. 16 is a graph showing the dependency of a thermoelectromotive force in a
30 thermoelectric converter element using a magnetic film 2 in which YIG (YaFesOn) was doped
with a different amount of an impurity of bismuth (Bi) (Bi was substituted for the Y sites), upon
the amount of doping impurity. Fig. 16 illustrates a case where YIG was doped with no
impurity.
Fig. 17 is a graph showing the dependency of a thermoelectromotive force in a
8
tbfcnoelectric converter element using a magnetic film 2 in which YIG (YsFesOn) was doped
with a different amount of an impurity of bismuth (Bi) (Bi was substituted for the Y sites), upon
the amount of doping impurity. Fig. 17 illustrates a case where YIG was doped with an
impurity such that the composition became Bio.sYzsFesOn.
5 Fig. 18 is a graph showing the dependency of a thermoelectromotive force in a
thermoelectric converter element using a magnetic film 2 in which YIG (YsFesO^) was doped
with a different amount of an impurity of bismuth (Bi) (Bi was substituted for the Y sites), upon
the amount of doping impurity. Fig. 18 illustrates a case where YIG was doped with an
impurity such that the composition became BiY2Fe50i2.
10 Fig. 19 is a graph showing the relationship between an external magnetic field and a
thermoelectromotive force of a thermoelectric converter element using a magnetic film 2 in
which an impurity of Bi was added to YIG (YsFesOn) such that the composition became
(BiY2Fe5012).
Fig. 20 is a graph showing the relationship between an external magnetic field and a
15 thermoelectromotive force of a thermoelectric converter element using a magnetic film 2 in
which an impurity of Ce was added to YIG (YsFesO^) such that the composition became
(CeY2Fe50i2).
Fig. 21 is a graph showing the relationship between an external magnetic field and a
thermoelectromotive force of a thermoelectric converter element using a magnetic film 2 in
20 which an impurity of La was added to YIG (YsFesO^) such that the composition became
(LaY2Fe5012).
Fig. 22 is a diagram explanatory of the phonon drag effect of spin currents in a
thermoelectric converter element 1.
Fig. 23 is a schematic diagram of an apparatus 100 used for an AD method (aerosol
25 deposition method).
Fig. 24 is a diagram modeling a SEM image of a surface of a Bi:YIG film produced by
an AD method. Fig. 24 models an image in a case where particulates were perpendicularly
incident.
Fig. 25 is a schematic diagram of an apparatus 100 used for an AD method (aerosol
30 deposition method).
Fig. 26 is a diagram modeling a SEM image of a surface of a Bi: YIG film produced by
an AD method. Fig. 26 models an image in a case where particulates were incident in an
inclined state of 25 degrees from the vertical position (the state shown in Fig. 25).
Fig. 27 is a perspective view showing a layered body of a Bi: YIG film/a GGG substrate
9
pgMuced by a Pt film/AD method.
Fig. 28 is a graph showing the relationship between an external magnetic field and a
thermoelectromotive force of a sample shown in Fig. 27 when a temperature gradient was varied.
Fig. 29 is a perspective view showing a layered body of a Bi: YIG film/a glass substrate
5 produced by a Pt film/AD method.
Fig. 30 is a graph showing the relationship between an external magnetic field and a
thermoelectromotive force of a sample shown in Fig. 29.
Fig. 31 is a diagram showing a thermoelectric converter element la of Example 3.
Fig. 32 is a graph showing the relationship between a magnetic field and a
10 thermoelectromotive force of a thermoelectric converter element 1 a of Example 3.
Fig. 33 is a diagram showing a thermoelectric converter element la of Example 4.
Fig. 34 is a graph showing the relationship between a magnetic field and a
thermoelectromotive force of a thermoelectric converter element la of Example 4.
15 Mode(s) for Carrying Out the Invention:
Preferred embodiments of the present invention will be described in detail below based
upon the drawings.
First, a first embodiment of the present invention will be described in detail with
reference to Figs. 1 to 6.
20 As shown in Fig. 1, a thermoelectric converter element 1 comprises a substrate 4, a
magnetic film 2 held on the substrate 4 for generating spin currents from a temperature gradient,
and an electrode 3 provided on the magnetic film 2 for deriving a thermoelectromotive force
from the spin currents using the inverse spin Hall effect.
Furthermore, the thermoelectric converter element 1 is formed such that terminals 7 and
25 9 for deriving a thermoelectromotive force can be mounted on two points of the electrode 3.
Those terminals 7 and 9 constitute a thermoelectromotive force output portion.
Moreover, the thermoelectric converter element 1 has a temperature gradient application
portion 11, as needed, for providing a temperature gradient to the magnetic film 2.
Furthermore, the thermoelectric converter element 1 comprises a magnetization portion
30 13, as needed, for magnetizing the magnetic film 2.
The substrate 4 is not limited to any specific material or structure as long as it can
support the magnetic film 2 and the electrode 3. For example, the substrate 4 may use a
substrate made of a material such as Si, glass, alumina, sapphire, gadolinium gallium garnet
(GGG), or polyimide. The shape of the substrate 4 does not need to be a plate-like shape, and
10
tijjMeubstrate 4 may comprise a structure having curves or unevenness. Furthermore, a building
or the like may directly be used as the substrate 4.
The magnetic film 2 includes a polycrystalline magnetic material having at least one
magnetization direction A. The first embodiment assumes that the magnetic film 2 has
5 magnetization in one direction parallel to its film surface (the magnetization direction has at least
a component parallel to the film surface). The magnetic film 2 exhibits the thermoelectric
effects more efficiently if it is made of a material having a lower thermal conductivity.
Therefore, it is preferable to use a magnetic insulator for the magnetic film 2. For example,
magnetic oxides such as garnet ferrite (yttrium iron ferrite) or spinel ferrite may be applied to
10 such a material.
A material in which an impurity such as Bi has been substituted for part of yttrium sites
of garnet ferrite may be used for the magnetic film 2. The matching of energy levels between
the magnetic film 2 and the electrode 3 will be improved when an impurity is substituted for
yttrium sites. Therefore, it may be possible to increase the efficiency of deriving spin currents
15 at an interface and thus improve the thermoelectric conversion efficiency.
One of specific examples of the composition is yttrium iron garnet doped with Bi
represented by Bi*Y3-xFe50i2 (0.5
X = 150 um. Thus, the
5 thermoelectromotive force (output voltage) Fdoes not increase any more.
Accordingly, in this case, the aforementioned characteristic thickness tc, i.e., the
thickness tc of the magnetic material film at which the thermoelectromotive force is saturated
under the conditions of a constant temperature difference applied between the upper and lower
surface of the element, can be defined so that tc = 3X.
10 However, the characteristic thickness tc at which the thermoelectromotive force is
saturated may not be determined merely by the magnon diffusion length X in a case where there
are other energy relaxation factors or in a case of an element structure in which another degree of
freedom such as phonons is involved.
The foregoing is summarized as follows: From the viewpoint of higher efficiency and
15 lower cost, the film thickness t of the magnetic film 2 should preferably be set to be about the
characteristic thickness tc at which the output voltage Fis saturated along with an increased
thickness of the magnetic material film.
Nevertheless, for an application in which reduction of variations in element
performance due to fluctuation of the film thickness of the magnetic material is important, such
20 as an application for a large-area deposition, it is preferable to design an element with a
relatively large film thickness of the magnetic material with which the thermoelectromotive force
is almost saturated. From this point of view, the thickness t of the magnetic material film
should preferably be set to be at least tc at which the thermoelectromotive force Fis substantially
saturated.
25 Meanwhile, in view of material saving (i.e., cost reduction), the film thickness at which
the output is completely saturated may be derived from the calculation results of Figs. 3 and 4.
As a result, it is preferable to set the thickness t of the magnetic material film to be not more than
5tc
In this manner, in consideration of power generation use in which highly efficient
30 conversion is of importance, the film thickness t of the magnetic film 2 is preferably in a range
between tJ5 and 5tc in order to achieve possible conversion performances.
Next, the thickness of the substrate 4 will be described below.
The lattice-magnon temperature difference ATmp at the interface between the magnetic
film 2 and the electrode 3 (and the thermoelectromotive force Vproportional to ATmp) depends
15
n^k>nly upon the magnetic film 2, but also upon parameters of the substrate 4. The following
description assumes an example under conditions that the magnon diffusion length X = 50 urn
(the characteristic thickness tc = 150 urn), the magnetic material film thickness t = 50 urn, and
the temperature difference between the upper and lower surfaces of the element AT = 10 K, and
5 examines the dependency of the lattice-magnon temperature difference ATmp of the
thermoelectric converter element 1 upon some substrate parameters.
First, Fig. 5 shows the dependency of the lattice-magnon temperature difference ATmp
upon the thickness D of the substrate in a case where the thermal conductivity Ksub of the
substrate 4 was equal to the thermal conductivity K/,im of the magnetic film 2 (Kf,im = Ksub). As
10 shown in Fig. 5, under the conditions that the temperature difference AT between the upper and
lower surfaces of the element is held constant, a temperature difference applied to a portion of
the magnetic film 2 (i.e., a temperature gradient in the magnetic film 2) increases as the thickness
D of the substrate 4 is reduced. As a result, the lattice-magnon temperature difference ATmp
increases at the interface between the magnetic film 2 and the electrode 3. In other words, as
15 the thickness D of the substrate 4 is smaller, the resultant thermoelectromotive force V becomes
larger.
Under the same conditions that the magnon diffusion length X = 50 um (the
characteristic thickness tc = 150 um), the magnetic material film thickness t = 50 um, and the
temperature difference between the upper and lower surfaces of the element AT= 10 K, now the
20 thickness of the substrate is fixed so that D = 0.5 mm. In this case, effects of the thermal
conductivity Ksub of the substrate 4 are examined. Fig. 6 shows the dependency of the
lattice-magnon temperature difference ATmp upon the "ratio KsublKfiim of the thermal conductivity
of the substrate 4 to the thermal conductivity of the magnetic film 2." As shown in Fig. 6,
under the condition that the temperature difference AT between the upper and lower surfaces of
25 the element is held constant, the temperature difference applied to a portion of the magnetic film
2 (i.e., the temperature gradient in the magnetic film 2) increases as the thermal conductivity Ksut
of the substrate 4 is increased. As a result, the lattice-magnon temperature difference ATmp
increases at the interface between the magnetic film 2 and the electrode 3. In other words, as
the thermal conductivity Ksub of the substrate 4 is higher as compared to the thermal conductivity
30 Kfiim of the magnetic film 2, the resultant thermoelectromotive force V becomes larger.
In this manner, the thickness D of the substrate 4 should preferably be as small as
possible in order to obtain a larger thermoelectromotive force. The thermal conductivity Ksub of
the substrate 4 should preferably be higher than the thermal conductivity Kf,im of the magnetic
film 2.
16
dk However, if the thickness D of the substrate 4 is extremely small or the thermal
conductivity Ksub of the substrate 4 is extremely high in practical thermoelectric power generation,
then it may be difficult to hold the temperature difference A T between the upper and lower
surfaces of the element. Furthermore, in some applications, the thickness of the substrate
5 should be increased to a certain degree in order to ensure the reliability of the element.
Therefore, those substrate parameters should properly be designed in consideration of the
balance between the thermoelectromotive force and the temperature difference AT, required
strength of the element, and the like.
According to Fig. 6, when the thermal conductivity Ksub of the substrate 4 is held
10 constant, a larger thermoelectromotive force Fcan be obtained as the thermal conductivity Kf,im
of the magnetic film 2 is lowered. According to the present invention, the magnetic film 2 is
formed of a polycrystalline insulator. Therefore, the crystallinity of the magnetic film 2 can be
controlled by a production method of the magnetic film 2. Accordingly, a higher output of
thermoelectric conversion can be achieved by optimizing the crystallinity of the magnetic film 2
15 so as to suppress phonon conduction.
In this manner, according to the first embodiment, the thermoelectric converter element
1 includes the substrate 4, the magnetic film 2 provided on the substrate 4 with a certain
magnetization direction A and formed of a polycrystalline magnetically insulating material, and
the electrode 3 provided on the magnetic film 2 with a material exhibiting the spin-orbit
20 interaction. When a temperature gradient is applied to the magnetic film 2, spin currents are
generated so as to flow from the magnetic film 2 toward the electrode 3. Thus, a current I is
generated in a direction perpendicular to the magnetization direction A of the magnetic film 2 by
the inverse spin Hall effect in the electrode 3.
Therefore, there can be provided a thermoelectric converter element that can achieve
25 both of high efficiency and low cost.
Specifically, since the magnetic film 2 is formed of a polycrystalline magnetically
insulating thin film, it can be deposited on a larger area at a low cost with high production
efficiency by using a coating or printing process. Furthermore, polycrystalline magnetic
insulators can remarkably suppress both of heat conduction by electrons and heat conduction by
30 phonons, unlike metals, semiconductors, and monocrystalline magnetic insulators. Therefore,
even a thin film of a polycrystalline magnetic insulator has high thermal insulation properties.
In other words, a polycrystalline magnetic insulator has such properties that it is unlikely to
release heat and can readily hold a temperature difference between the front face and the rear
face of the thermoelectric converter element.
17
^L Next, a second embodiment of the present invention will be described in detail below
with reference to Fig. 7.
In the second embodiment, a material having coercivity is used as the magnetic film 12
of the first embodiment.
5 In the second embodiment, components having the same functions as those in the first
embodiment are denoted by the same reference numerals. Thus, the following description
focuses on differences between the second embodiment and the first embodiment.
As shown in Fig. 7, a thermoelectric converter element la comprises a substrate 4, a
magnetic film 12 held on the substrate 4, and an electrode 3 provided on the magnetic film 12.
10 The magnetic film 12 is a material having coercivity in a magnetization direction C (a
direction perpendicular to the film thickness direction in this example). A magnetic field was
applied to the magnetic film 12 with use of the magnetization portion 13 (see Fig. 1) or the like,
so that the magnetic film 12 has been magnetized in the magnetization direction C.
In this manner, use of a pre-magnetized material as the magnetic film 12 allows the
15 magnetic film 12 to hold spontaneous magnetization in the magnetization direction C.
Therefore, a thermoelectromotive force can be generated by the spontaneous magnetization of
the magnetic film 12 even in an environment of zero magnetic field in which no magnetic field is
applied from the exterior of the element.
Furthermore, once the magnetic film 12 has spontaneous magnetization, the
20 magnetization portion 13 (see Fig. 1) becomes unnecessary.
Specific materials for the magnetic film 12 include a material produced by substituting
an impurity for part of the iron sites of garnet ferrite to enhance the coercivity.
In this manner, according to the second embodiment, the thermoelectric converter
element la includes the substrate 4, the magnetic film 12 provided on the substrate 4 with a
25 certain magnetization direction C and formed of a polycrystalline magnetically insulating
material, and the electrode 3 provided on the magnetic film 12 with a material exhibiting the
spin-orbit interaction. When a temperature gradient is applied to the magnetic film 12, spin
currents are generated so as to flow from the magnetic film 12 toward the electrode 3. Thus, a
current lis generated in a direction perpendicular to the magnetization direction C of the
30 magnetic film 12 by the inverse spin Hall effect in the electrode 3.
Accordingly, the second embodiment exhibits the same advantageous effects as the first
embodiment.
Furthermore, according to the second embodiment, the magnetic film 12 has coercivity
in the magnetization direction C.
18
^L Therefore, no application of an external magnetic field is necessary upon the
thermoelectric conversion. Accordingly, there can be provided a thermoelectric converter
element that can achieve higher efficiency and lower cost as compared to the thermoelectric
converter element of the first embodiment.
5 Next, a third embodiment of the present invention will be described in detail below with
reference to Fig. 8.
In the third embodiment, multiple sets of the magnetic films 2 and the electrodes 3 of
the first embodiment are stacked.
In the third embodiment, components having the same functions as those in the first
10 embodiment are denoted by the same reference numerals. Thus, the following description
focuses on differences between the third embodiment and the first embodiment.
As shown in Fig. 8, a thermoelectric converter element lb comprises a substrate 4 and a
power generation portion 5 held on the substrate 4 in which magnetic films 2 and electrodes 3
are alternately stacked.
15 In this manner, the magnetic films 2 and the electrodes 3 are alternately stacked.
Therefore, a thermoelectromotive force Fcan be derived from each of the stacked electrodes 3.
Furthermore, when those electrodes 3 are connected in series to sum the thermoelectromotive
forces V, a large thermoelectromotive force Vtotai can be obtained as a whole.
The magnetic films 2 may be formed of a material having coercivity as with the
20 magnetic film 12 of the second embodiment. In such a case, the thermoelectric converter
element lb can generate power by the spontaneous magnetization of the magnetic films 12 even
in an environment having no external magnetic field.
Furthermore, a spacer layer may be interposed in the above stacking structure as needed.
For example, non-magnetic insulator such as a Si02 layer may be used as the spacer layer.
25 Moreover, when polyolefin such as polyethylene and polypropylene or polyester such as PET
(PolyEthylene Terephthalate) and PEN (PolyEthylene Naphthalate) is used for the spacer layer,
the spacer layer can be formed by a printing process.
Here, one of such multilayered thermoelectric converter elements has been known as a
conventional thermoelectric converter element based upon a thermocouple, for example, as
30 disclosed in JP-A 2003-92435. However, the objectives and advantageous effects of the
thermoelectric converter element lb according to the third embodiment are essentially different
from those of the conventional thermoelectric converter element.
Specifically, the conventional multilayered thermoelectric converter element primarily
aims at "improvement of the user's convenience" and "optimization of the performance" by
19
s^king a plurality of thermoelectric materials having different optimal operational temperatures
so as to enable power generation in a wide temperature range from a high temperature to a low
temperature. Conversely, the multilayering is not so effective in a case where the power
generation performance of thermoelectric materials does not depend so much upon the
5 temperature or in a case where a temperature range to be used is limited. In other words, when
the thickness of thermoelectric modules or the temperature difference to be applied is the same, a
module using a thick single layer of a thermoelectric material and a module stacking a plurality
of thin thermoelectric materials do not make much difference in thermoelectric conversion
efficiency.
10 In contrast, according to a thermoelectric converter element of the present invention, the
thermoelectromotive force is saturated if the magnetic film 2 has a thickness greater than a
certain value, or a "characteristic thickness tc." An element formed by stacking a plurality of
thin magnetic films 2 having a thickness not more than the characteristic thickness tc and
electrodes 3 can demonstrate higher thermoelectric conversion performance, as a whole, than an
15 element formed of a single layer of a magnetic film 2 having a thickness not less than the
characteristic thickness tc and an electrode 3.
Therefore, the preferable design guidelines for a thermoelectric converter element of the
third embodiment are as follows: (1) First, the film thickness of the substrate 4 and the power
generation portion 5 that is required for a specific application is designed. (In order to hold a
20 temperature difference for thermoelectric power generation, an element requires a certain
minimum film thickness. Furthermore, the thickness of the substrate 4 or the like is determined
upon the required reliability or durability. Depending upon the application, the substrate 4 may
be made as thin as possible, or an element may be formed without use of the substrate 4.) (2)
Next, the design film thickness required in the power generation portion 5 is compared to the
25 characteristic thickness tc of the magnetic material. (2A) If the design film thickness of the
power generation portion 5 is not more than the characteristic thickness tc, then the power
generation portion 5 is formed by a single layer of a magnetic film 2 and an electrode 3. (2B) If
the design film thickness of the power generation portion 5 is not less than the characteristic
thickness tc, then the power generation portion 5 is formed by stacking a plurality of magnetic
30 films 2 and electrodes 3. (3) In the case where the power generation portion 5 is multilayered
as in (2B), the film thickness of the magnetic film 2 in each of the layers should preferably set to
be not more than the characteristic thickness tc in view of higher efficiency. Nevertheless, the
number of manufacturing processes increases when many thin magnetic films are stacked.
Therefore, it is the most preferable to set the film thickness of the magnetic film 2 in each of the
20
tapirs to be about the characteristic thickness tc in consideration of simplification of the
manufacturing processes.
With the above design, the most efficient thermoelectric conversion can be achieved
under conditions for a specific application or power generation.
5 In this manner, according to the third embodiment, the thermoelectric converter element
lb includes the substrate 4, the magnetic films 2 provided on the substrate 4 with a certain
magnetization direction A and formed of a polycrystalline magnetically insulating material, and
electrodes 3 provided on the magnetic films 2 with a material exhibiting the spin-orbit
interaction. When a temperature gradient is applied to the magnetic films 2, spin currents are
10 generated so as to flow from the magnetic films 2 toward the electrodes 3. Thus, a current / is
generated in a direction perpendicular to the magnetization direction A of the magnetic films 2
by the inverse spin Hall effect in the electrodes 3.
Accordingly, the third embodiment exhibits the same advantageous effects as the first
embodiment.
15 Furthermore, according to the third embodiment, the thermoelectric converter element
lb comprises the power generation portion 5 in which the magnetic films 12 and the electrodes 3
are alternately stacked on each other.
Therefore, a thermoelectromotive force Fcan be derived from each of the stacked
electrodes 3. Furthermore, when those electrodes 3 are connected in series to sum the
20 thermoelectromotive forces V, a large thermoelectromotive force Vtotai can be obtained as a
whole.
Examples
The present invention will be described in greater detail based upon some examples.
[Example 1]
25 A thermoelectric converter element 1 according to the first embodiment was produced,
and a thermoelectromotive force of the thermoelectric converter element 1 was evaluated.
Specific procedures were as follows.
Fig. 9 shows an example of the thermoelectric converter element produced. A
30 substrate (111) surface of gadolinium gallium garnet (with composition of GdsGasO^;
hereinafter referred to as "GGG") manufactured by Saint-Gobain K. K. was prepared. The
thickness of the substrate was 0.7 mm, and the substrate had a rectangular shape with planar
dimension of 2 mm * 4 mm.
Then a film of yttrium iron garnet (with composition of BiY2FesOi2; hereinafter referred
21
t^Kf "Bi:YIG") in which Bi had been substituted for part of the Y sites was deposited as a
magnetic film 2 on the GGG substrate by a metal organic decomposition method (MOD
method).
Specifically, a MOD solution with a mole fraction of Bi:Y:Fe = 1:2:5 that had been
5 manufactured by Kojundo Chemical Lab. Co., Ltd. was used. (Within this solution, raw metal
materials were dissolved in acetic ester at a concentration of 3 %.) (1) First, this solution was
applied onto the GGG substrate at a revolving speed of 1,000 rpm for 30 seconds by a
spin-coating method. (2) The GGG substrate was dried with a hot plate of 150°C for 5 minutes.
(3) Then the GGG substrate was heated at 550°C in an electric furnace for 5 minutes and thus
10 temporarily sintered. (4) Finally, the GGG substrate was sintered at 720°C in the same electric
furnace for 14 hours. Thus, a Bi:YIG film having a film thickness of about 65 nm was formed
on the GGG substrate.
Next, a Pt electrode having a film thickness of 10 nm was deposited as an electrode 3 on .
the Bi:YIG film by a sputtering method. Thus, a thermoelectric converter element 1 was
15 completed. A distance between the terminals 7 and 9 of the electrode 3 was set to be 4 mm.
A cross-section of the complete thermoelectric converter element 1 was observed with
use of a transmission electron microscope (TEM). As a result, it was confirmed that a
crystalline film of Bi:YIG that had less defects or grain boundaries was formed so as to achieve
lattice matching with the GGG (111) surface as shown in Fig. 9.
20
Next, a varying magnetic field //was applied to the produced sample within a range of
-120 Oe to +120 Oe (1 Oe = 79.577 A/m) with use of an electromagnet. Furthermore, a heat
sink made of Cu was provided on one of an upper end and a lower end of the thermoelectric
converter element 1, which was used for a low-temperature side. A heater was provided on the
25 other end of the thermoelectric converter element 1, which was used for a high-temperature side.
Temperature differences AT= 1 K, 2 K, and 3 K were applied, and voltages
(thermoelectromotive forces) V between the terminals 7 and 9 of the electrode 3 were measured.
Fig. 10 shows the relationship between the magnetic field and the thermoelectromotive
force of the thermoelectric converter element 1, and Fig. 11 shows the relationship between the
30 temperature difference AT and the thermoelectromotive force of the thermoelectric converter
element 1.
As is apparent from Fig. 10, the magnetic field H served to reverse the magnetization of
the magnetic film 2. Thus, it was found that the sign of the thermoelectromotive force Fis
reversed by the reversed magnetization.
22
^gfe Furthermore, as shown in Fig. 11, it was found that the thermoelectromotive force V
increases in proportion to AT.
5 Next, the revolving speed of the spin-coating application described in the above (1) was
varied in a range of 1,000 rpm to 5,000 rpm so as to vary the film thickness tyiG of the magnetic
film 2. Then the dependency of the thermoelectromotive force of the element upon the film
thickness was examined. For production, the element was dried with a hot plate at 150°C for 5
minutes after the spin-coating process. Then the element was heated at 550°C in an electric
10 furnace for 5 minutes and thus temporarily sintered. Finally, the element was sintered at 720°C
in the same electric furnace for 4 hours.
For evaluation of the thermoelectromotive force, while a magnetic field H was varied in
a range of-120 Oe to +120 Oe (1 Oe = 79.577 A/m), a thermoelectromotive force was measured
in a state in which the temperature difference was fixed so that AT = 3 K. Thus, the
15 dependency of the thermoelectromotive force upon the film thickness (of the magnetic film 2)
was measured. Fig. 12 shows the results plotting thermoelectromotive forces with the
horizontal axis representing the film thickness tyiG of Bi:YIG. It was seen that the
thermoelectromotive force V increased substantially in proportion to the film thickness tyiG of the
magnetic film 2.
20
Next, the revolving speed of the spin-coating application was set to be 1,000 rpm, and
an MOD solution was overlaid a plurality of times. Thus, those experiments were conducted to
vary the film thickness of the magnetic film 2. Specifically, the processes of (1) spin-coating,
25 (2) drying at 170°C, and (3) temporarily sintering at 550°C were repeated N times (N= 1 to 3) so
as to form a thick film. Finally, sintering at 680°C for 14 hours was conducted to form a
Bi:YIG magnetic film.
Figs. 13 and 14 show the evaluation results of the thermoelectric conversion
characteristics of this element.
30 Fig. 13 shows the thermoelectromotive forces of the element subjected to single, double,
and triple overlay coatings with the horizontal axis representing the external magnetic field H.
On the other hand, Fig. 14 shows the measurement results of the same thermoelectromotive
forces with the horizontal axis representing the film thickness. Those results revealed that the
overlay coating doubles and triples the film thickness and that the thermoelectromotive force
23
ajfcincreases in proportion to the increased film thickness.
Figs. 13 and 14 only show the results of the experiments where the number of overlay
coatings N was up to three. However, even if TV is not less than three, the similar effects of a
thermoelectromotive force increased by an increased film thickness are anticipated.
5 As shown by a series of experiments described above, when the magnetic material film
thickness t (tyiG) is less than the characteristic thickness tc (t < tc), an increased output of the
thermoelectric converter element can be achieved by increasing the film thickness of the
magnetic material with control of the revolving speed of the spin-coating for application and
deposition, overlay coating, or the like.
10
Next, a thermoelectric converter element 1 comprising a structure shown in Fig. 15 was
produced. The relationship between the amount of a doping impurity of bismuth (Bi) in
Bi:YIG used for the magnetic film 2 and the thermoelectromotive force was evaluated.
Specific procedures were as follows.
15 First, a GGG substrate having a thickness of 0.7 mm and a planar dimension of 2 mm *
6 mm was prepared as a substrate 4, and Bi:YIG in which YIG (YaFesO^) had been doped with
different amounts of an impurity of bismuth (Bi) (Bi had been substituted for the Y sites) was
deposited as a magnetic film 2 on the substrate 4.
Specifically, Bi:YIG having three types of composition BixY3-^FesOi2 where x = 0, x =
20 0.5, and x = 1.0 was deposited with a thickness of 160 nm under sintering conditions of 720°C
and 14 hours by a metal organic decomposition method (MOD method).
Next, a Pt electrode was deposited as an electrode 3 so as to have a film thickness of 10
nm by a sputtering method. Thus, samples were completed.
Then a varying magnetic field H was applied to those samples within a range of-120
25 Oe to +120 Oe (1 Oe = 79.577 A/m). The thermoelectromotive force was measured in a state in
which the temperature difference was fixed so that AT= 3 K. Thus, the dependency of the
thermoelectromotive force upon the amount of doping impurity was evaluated.
The results are shown in Figs. 16 to 18.
As is apparent from Figs. 16 to 18, the thermoelectric conversion performance was
30 greatly improved by substituting bismuth (Bi) for the sites of yttrium (Y). This is conceivably
because the matching of energy levels between the magnetic film 2 and the electrode 3 (Pt) was
improved by substituting bismuth (Bi) for the yttrium (Y) sites, so that the derivation efficiency
of spin currents at an interface between the magnetic film 2 and the electrode 3 was increased.
From the above results, it was found that it is preferable to use, as the magnetic film 2, a
24
^Mk film (BixY3-^FesOi2) in which an impurity of Bi has been doped, in order to achieve an
increased efficiency of thermoelectric conversion.
From the results shown in Figs. 16 to 18, the doping amount x should preferably satisfy
that x> 0.5. However, if the amount of doping Bi is excessively increased, the magnetic film
5 may become unstable. Therefore, it is preferable to satisfy that 0.5 < JC < 1.5.
From the above experiments, effects of enhancing the thermoelectromotive force
through Bi doping were confirmed. Here, thermoelectric converter elements using YIG in
which YIG had been doped with an impurity other than Bi were also evaluated. Specific
10 procedures were as follows.
First, GGG substrates each having a thickness of 0.7 mm and a planar dimension of 2
mm x 6 mm were prepared as substrates 4, and magnetic films 2 of X: YIG in which YIG
(YsFesOn) had been doped with three different impurities X (X = Bi, Ce, and La) were
respectively deposited on the substrates 4. The impurity X was substituted for the yttrium (Y)
15 sites of YIG so as to form a composition of (XY2)FesOi2.
One of specific deposition methods is as follows: X: YIG was deposited with a
thickness of 65 nm under sintering conditions of 680°C and 14 hours in the same manner as
described above by a metal organic decomposition method (MOD method). Then a Pt
electrode was deposited as an electrode 3 so as to have a film thickness of 10 nm by a sputtering
20 method. Thus, samples were completed.
Then a varying magnetic field //was applied to those samples within a range of-180
Oe to +180 Oe (1 Oe = 79.577 A/m). The thermoelectromotive force was measured in a state in
which the temperature difference was fixed so that AT= 16.5 K. Thus, the dependency of the
thermoelectromotive force upon the amount of doping impurity was evaluated.
25 The results are shown in Figs. 19 to 21.
As is apparent from Figs. 19 to 21, the largest thermoelectromotive force signal was
measured in the case where X = Bi. For the samples where X = Ce and La, larger
thermoelectromotive forces could be obtained as compared to YIG that had not been doped with
an impurity as shown in Fig. 16. In other words, effects of enhancing the thermoelectromotive
30 force were clearly obtained in cases where an impurity other than Bi had been substituted for the
Y sites.
This experiment revealed that an impurity X should preferably be substituted for the Y
sites in order to obtain a large thermoelectromotive force. Particularly, it was found that X
should preferably be Bi.
25
! M% Thus, the aforementioned examples illustrate that a thermoelectric converter element
can be configured with a thin film of a polycrystalline magnetic insulator produced by a simple
process of coating and sintering. It was found that the area of the thermoelectric converter
element of Example 1 can further be increased with ease and that a thermoelectric converter
5 element having high productivity can be achieved.
In the experiments illustrated in Figs. 9 to 11, a temperature difference AT = 3 K was
applied between the upper surface and the bottom surface of the element, and a
thermoelectromotive force was measured. Meanwhile, the film thickness tyiG of the magnetic
10 insulator (Bi:YIG) layer on the GGG substrate having a thickness tGGG = 0.7 mm was as thin as
65 nm. Therefore, a temperature difference ATYIG applied to a magnetically insulating portion
(film thickness portion of Bi:YIG) in which spin currents are thermally driven is supposed to be
about several mK even at the highest estimate and to be extremely small. Nevertheless,
according to the experiment results shown in Fig. 10, the thermoelectromotive force was
15 measured on the order of uV. This experiment result showing a relatively large
thermoelectromotive force strongly suggests contribution of "phonon drag effect," in which the
thermoelectric effect is enhanced through interaction with phonons in the substrate, in addition to
the spin Seebeck effect in the electrode 3/the magnetic film 2.
The phonon drag refers to a phenomenon in which spin currents in a structure of an
20 electrode and a magnetic film interact non-locally with phonons of an overall element including
a substrate (Reference: Applied Physics Letter 97, 252506). In consideration of this phonon
drag process, spin currents in a very thin film as in Example 1 are sensitive to a temperature
distribution in a substrate that is much thicker than the thin film, through the non-local
interaction with the phonons. Therefore, the effective thermoelectric effects greatly increase.
25 Specifically, as shown in Fig. 22, not only the temperature difference ATYIG applied to a
thin magnetic insulator (film thickness portion of Bi:YIG), but also the temperature difference
ATQQQ applied to a thick substrate contributes to the thermal driving of the spin currents. As a
result, a larger thermoelectromotive force is generated in the electrode.
While validation of the fundamental principle of such a phonon drag effect has been
30 reported, there have been no specific proposals for methods of designing large-area and low-cost
thermoelectric devices using this effect. In the structure of the present invention, use of this
phonon drag effect allows a thermoelectric conversion device to be mounted merely by
depositing a thin structure of an electrode and a magnetic film that has a thickness of 100 nm or
less on an inexpensive non-magnetic substrate. Therefore, costs for raw materials and other
26
r^gufacturing costs may remarkably be reduced as compared to a case where a bulk magnetic
material or the like is used. In addition, coating is used for a production process of a magnetic
insulator film as in Example 1. Accordingly, large-area devices can be manufactured with high
productivity.
5 Most of non-magnetic substrate materials can be produced at cost per volume that is not
more than 1/10 of those of crystalline magnetically insulating materials such as YIG. Therefore,
when a low-cost thermoelectric element using the phonon drag effect is designed, it is preferable
for the thickness (tyiG) of the magnetic material not to be more than 1/10 of the total thickness of
the electrode and the substrate.
10 The experiment results of Fig. 12 suggest that high thermoelectric performance cannot
be obtained if the thickness (tyiG) of the magnetic material is excessively small. Therefore, tyiG
should preferably be at least 50 nm.
(Preferable power generation method)
When power is actually generated with use of a thermoelectric converter element
15 comprising a stacked structure of a substrate, a magnetic insulator film, and the like as describe
above, a temperature difference is applied to the element while one surface of the element is used
for a high-temperature side, whereas the other surface of the element is used for a
low-temperature side. For example, one surface of the element (the high-temperature side) is
brought close to a heat source having a high temperature and is thus set at a temperature 7#.
20 The other surface of element (the low-temperature side) is air-cooled or water-cooled as needed
and set at a temperature TL. Thus, a temperature difference AT = TH - TL is generated.
At that time, if the temperature of the magnetic insulator portion (magnetic film 2)
exceeds the Curie temperature TQ in a thermoelectric converter element according to the present
invention, the spin Seebeck effect is impaired. As a result, an operation for power generation
25 cannot be performed. Therefore, when thermoelectric power generation is performed with use
of the element shown in Fig. 9, it is preferable to use a surface located away from the magnetic
insulator (the lower surface of the substrate in Fig. 9; the surface on which no magnetic film is
formed) for a high-temperature side and use a surface located near the magnetic insulator film
(the upper surface of the substrate in Fig. 9; the surface on which the magnetic film is provided)
30 for a low-temperature side. In order to ensure the operation for thermoelectric power
generation by the aforementioned temperature difference application method, at least the
low-temperature side should not exceed the Curie temperature of the magnetic insulator such that
Ti < TQ. However, the high-temperature side may exceed the Curie temperature if the
low-temperature side can properly be cooled so as to meet the above conditions. Therefore, the
27
(Ajiitions may be such that TL
20 Use of the aforementioned AD method allows a thermoelectric element to be formed on
a flexible substrate made of an organic resin material because the AD method does not require
high-temperature annealing. Therefore, it is possible to form a thermoelectric converter
element having flexibility.
Production of a flexible element using a substrate having flexibility was attempted.
25 First, a polyimide substrate manufactured by Ube Industries, Ltd. was prepared as a substrate 4. |
Next, as with Example 1, a film of yttrium iron garnet (with composition of
BiY2FesOi2; Bi: YIG) in which Bi had been substituted for part of the Y sites was deposited as a j
magnetic film 2 on the substrate 4 by an AD method. Specifically, Bi: YIG particulates having a diameter of 500 nm that had been
30 manufactured by KCM Corporation were prepared as a Bi:YIG material. Those Bi:YIG
particulates were packed into an aerosol generation container, and the polyimide substrate was
fixed on a holder in a deposition chamber.
Then the pressure of the deposition chamber was reduced to about 100 Pa in that state
•
by a rotary pump, so that a pressure difference was generated between the deposition chamber
30
3Athe aerosol generation container. Thus, the Bi:YIG particulates were drawn into the
deposition chamber and blown onto the polyimide substrate through a nozzle that was inclined at
25 degrees based upon the aforementioned oblique incidence method. The blown particulates
collided with the substrate at a speed of about 300 m/s. The collision energy at that time
5 allowed the particulates to be ground and re-coupled, so that Bi:YIG poly crystal was formed on
the substrate. A surface of the substrate was scanned two-dimensionally to deposit a uniform
Bi: YIG film on the substrate with a film thickness of 0.1 mm.
Next, an Au electrode was formed as an electrode 3 on the magnetic film 2 by an
electroless gold plating method. Specifically, a gold plating liquid containing a gold salt of
10 sodium gold sulfite that had been manufactured by Hitachi Chemical Co., Ltd. was used, and a
gold plating film of 50 nm was deposited with use of hypophosphite as a reducing agent.
By the above processes, a thermoelectric converter element 1 using polyimide as a
substrate could be produced.
Thus, use of a plastic substrate such as polyimide, which has high flexibility, allowed
15 formation of a flexible module, and a thermoelectric converter element that can be provided on
heat sources having various shapes could be achieved.
[Example 3]
A thermoelectric converter element la according to the second embodiment was
produced, and the thermoelectromotive force was evaluated. Specific procedures were as
20 follows.
First, a substrate (100) surface of gadolinium gallium garnet (GGG) manufactured by
NTT Electronics Corporation was prepared as a substrate 4. The substrate had a thickness of
0.7 mm and a planar dimension of 2 mm x 4 mm.
25 Next, yttrium iron garnet (with composition of BiY2Fe4GaOi2; hereinafter referred to as
Bi, Ga:YIG) in which Bi had been substituted for part of the Y sites and Ga had been substituted
for part of the Fe sites was deposited as a magnetic film 12 on the substrate 4 by a metal organic
decomposition method (MOD method).
Specifically, a MOD solution with a mole fraction of Bi:Y:Fe:Ga = 1:2:4:1 that had been
30 manufactured by Kojundo Chemical Lab. Co., Ltd. was used. (Within this solution, raw metal
materials were dissolved in acetic ester at a concentration of 3 %.) This solution was applied j
onto the GGG substrate at a revolving speed of 1,000 rpm for 30 seconds by a spin-coating [
method. The substrate was dried with a hot plate of 150°C for 5 minutes. Then the substrate I
was sintered at 720°C in an electric furnace for 14 hours. Thus, a Bi, Ga:YIG film having a
31
fjipthickness of about 160 nm was formed as a magnetic film 12 on the GGG substrate.
Next, a Pt electrode having a film thickness of 10 nm was deposited as an electrode 3 on
the magnetic film 12 by a sputtering method. Thus, a thermoelectric converter element la
comprising a structure illustrated in Fig. 31 was completed. A distance between the terminals 7
5 and 9 of the electrode 3 was set to be 4 mm. i
Next, a varying magnetic field H was applied to the produced thermoelectric converter
element la within a range of-120 Oe to +120 Oe (1 Oe = 79.577 A/m) with use of an
electromagnet. Furthermore, a heat sink made of Cu was provided on one of an upper end and
10 a lower end of the thermoelectric converter element 1, which was used for a low-temperature
side. A heater was provided on the other end of the thermoelectric converter element 1 a, which
was used for a high-temperature side. A temperature difference AT = 3 K was applied, and a
voltage (thermoelectromotive force) V between the terminals 7 and 9 of the electrode 3 was
measured. 1
15 Fig. 32 shows the measured relationship between the magnetic field and the
thermoelectromotive force.
As shown in Fig. 32, unlike the thermoelectric converter element 1, the magnetic film
12 (Bi, Ga:YIG) of the thermoelectric converter element la had coercivity. Therefore, the
dependency of the thermoelectromotive force Fupon the external magnetic field H demonstrated
20 hysteresis. Specifically, it was found that, once the element was magnetized in one direction by
the external magnetic field, it exhibited a finite thermoelectromotive force even though the j
magnetic field H returned to zero. j
This result reveals that, if the magnetic film 12 is magnetized beforehand, a
i
thermoelectromotive force can be generated by spontaneous magnetization of the magnetic film {
25 12 even in an environment where the magnetic field is zero. j
[Example 4] j
A thermoelectric converter element la was produced while a glass substrate was used as
a substrate 4 in Example 1, and the thermoelectromotive force was evaluated. Specific
procedures were as follows. 30 [
First, a silica glass substrate (having a thickness of 0.5 mm and a planar dimension of 2 mm x 4 mm) that had been manufactured by Optostar Ltd. was prepared as a substrate 4. A
film of yttrium iron garnet (Bi:YIG) in which Bi had been substituted for part of the Y sites was
deposited as a magnetic film 12 by a metal organic decomposition method (MOD method).
i
i
f
t
i
32
A . Specifically, a MOD solution with a mole fraction of Bi:Y:Fe = 1:2:5 that had been
manufactured by Kojundo Chemical Lab. Co., Ltd. was used. (Within this solution, raw metal
materials were dissolved in acetic ester at a concentration of 3 %.) This solution was applied
onto the silica glass substrate at a revolving speed of 1,000 rpm for 30 seconds by a spin-coating
5 method. The substrate was dried with a hot plate of 150°C for 5 minutes. Then the substrate
was sintered at 720°C in an electric furnace for 18 hours. Thus, a Bi:YIG film having a film
thickness of about 160 nm was formed as a magnetic film 12 on the GGG substrate.
Next, an Au electrode having a film thickness of 50 nm was deposited as an electrode 3
on the magnetic film 12 by a sputtering method. Thus, a thermoelectric converter element la
10 comprising a structure shown in Fig. 33 was completed. A distance between the terminals 7
and 9 of the electrode 3 was set to be 4 mm.
Next, a varying magnetic field //was applied to the produced thermoelectric converter
element la within a range of-120 Oe to +120 Oe (1 Oe = 79.577 A/m) with use of an
15 electromagnet. Furthermore, a heat sink made of Cu was provided on one of an upper end and
a lower end of the thermoelectric converter element la, which was used for a low-temperature
side. A heater was provided on the other end of the thermoelectric converter element la, which
was used for a high-temperature side. A temperature difference AT = 3 K was applied, and a
voltage (thermoelectromotive force) V between the terminals 7 and 9 of the electrode 3 was
20 measured.
Fig. 34 shows the measured relationship between the magnetic field and the
thermoelectromotive force.
As is apparent from Fig. 34, although the sample of Example 4 employed the same
Bi:YIG film as in Example 1, the dependency of the thermoelectromotive force Fupon the
25 external magnetic field H demonstrated hysteresis. Specifically, once the element was
magnetized in one direction by the external magnetic field, it exhibited a finite
thermoelectromotive force even though the magnetic field Hreturned to zero. In other words,
if the element is initialized at first (magnetized In a direction substantially perpendicular to a
direction in which a thermoelectromotive force is derived), then a thermoelectromotive force can
30 be generated by spontaneous magnetization of the magnetic film 12 even in an environment
where the magnetic field is zero. I
This is conceivably because the Bi:YIG film had coercivity as it was formed on the
silica glass substrate unlike Example 1 in which the Bi: YIG film was formed on the GGG
substrate.
"i~
33 ;
£fc The above result reveals that, when a Bi:YIG film is formed on a silica glass substrate,
the Bi:YIG film has coercivity.
In the case of such a thermoelectric converter element formed on a glass substrate, cost
reduction and area increment are facilitated. Therefore, such a thermoelectric converter
5 element can be applied to power generation using temperature differences at a window or the
like between the inside and the outside of a room and to a display and the like.
[Example 5]
Production of a thermoelectric converter element la was attempted by using polyimide
as a substrate 4 and depositing a magnetic film 12 by an AD method. Specific procedures were
10 as follows.
First, a polyimide substrate manufactured by Ube Industries, Ltd. was prepared as a
substrate 4. A film of yttrium iron garnet (Bi, Ga:YIG) in which Bi had been substituted for
part of the Y sites and Ga had been substituted for part of the Fe sites was deposited as a
magnetic film 12 by an aerosol deposition method.
15 Specifically, Bi, Ga:YIG particulates having a diameter of 500 nm that had been
manufactured by KCM Corporation were prepared as a Bi, Ga:YIG material.
Then those Bi, Ga: YIG particulates were packed into an aerosol generation container,
i
and the polyimide substrate was fixed on a holder in a deposition chamber.
Subsequently, the pressure of the deposition chamber was reduced to about 100 Pa in
20 that state by a rotary pump, so that a pressure difference was generated between the deposition
chamber and the aerosol generation container. Thus, the Bi, Ga: YIG particulates were drawn
into the deposition chamber and blown onto the polyimide substrate through a nozzle. The
blown particulates were ground and re-coupled by the collision energy upon collision with the
•
substrate. Thus, Bi, Ga:YIG polycrystal was formed on the substrate. A surface of the
25 substrate was scanned two-dimensionally to deposit a uniform Bi, Ga:YIG film on the substrate
with a film thickness of 0.1 mm.
Next, Au was formed as an electrode 3 on the magnetic film 12 by an electroless gold
plating method. Specifically, a gold plating liquid containing a gold salt of sodium gold sulfite
that had been manufactured by Hitachi Chemical Co., Ltd. was used, and a gold plating film of
i
30 50 nm was deposited with use of hypophosphite as a reducing agent. Thus, a thermoelectric [
converter element la could be produced.
Thus, use of a plastic substrate such as polyimide, which has high flexibility, could
achieve a flexible thermoelectric converter element that can be provided on heat sources having
various shapes.
j
i'
34
£l< Additionally, use of an AD method allows high-speed deposition of a thick film of 10
um or more. A film with a film thickness around the characteristic thickness tc can be formed
in a short period of time. Therefore, it is possible to achieve a thermoelectric converter element
with high efficiency and high productivity.
5 [Example 6]
Production of a thermoelectric converter element lb according to the third embodiment
was attempted. Specific procedures were as follows.
First, a polyimide substrate was used as a substrate 4. A yttrium iron garnet BkYIG
film (with composition of BiY2FesOi2) in which Bi had been substituted for part of the Y sites
10 was deposited as a magnetic film 2 by an aerosol deposition method.
Specifically, Bi:YIG particulates having a diameter of 300 nm that had been
manufactured by Toda Kogyo Corporation were prepared as a Bi:YIG material. Those BkYIG
particulates were packed into an aerosol generation container, and the polyimide substrate was
fixed on a holder in a deposition chamber.
15 Subsequently, the pressure of the deposition chamber was reduced to about 100 Pa in
that state by a rotary pump, so that a pressure difference was generated between the deposition
chamber and the aerosol generation container. Thus, the BkYIG particulates were drawn into
the deposition chamber and blown onto the polyimide substrate through a nozzle. The blown
particulates were ground and re-coupled by the collision energy upon collision with the substrate.
20 Thus, BkYIG polycrystal was formed on the substrate. A surface of the substrate was scanned
two-dimensionally to deposit a uniform BkYIG film on the substrate with a film thickness of 0.1
mm.
Next, Au was formed as an electrode 3 on the magnetic film 12 by an electroless gold
plating method. Specifically, a gold plating liquid containing a gold salt of sodium gold sulfite
• 25 that had been manufactured by Hitachi Chemical Co., Ltd. was used, and a gold plating film of
50 nm was deposited with use of hypophosphite as a reducing agent.
Next, deposition of the magnetic film 2 and formation of the electrode 3 were repeated
so as to produce a power generation portion 5 comprising a four-layer stacked structure of
Au/BkYIG.
30 As a result, a thermoelectric converter element lb comprising a stacked structure of the
magnetic films 2 and the electrodes 3 could be produced.
Industrial Applicability:
Examples of applications of the present invention include power sources for feeding a
35
^fciinal, a sensor, or the like.
In the above embodiments, the thermoelectric converter elements 1,1a, and lb are (
applied to thermoelectric power generation for deriving a current or a voltage from a temperature
gradient. However, the present invention is not limited to those embodiments. For example,
5 the thermoelectric converter elements 1,1a, and lb may be used for a thermal sensor that detects
a temperature, an infrared ray (by disposing an absorbing film or the like at a proximate location),
or the like. In principle, the thermoelectric converter elements 1,1a, and lb may be used in a
reversed manner to the aforementioned use as a Peltier element that generates a temperature
gradient by supplying a current to the electrode 2 from an external source.
10 In the above embodiments, the magnetic film 2 is deposited on the substrate 4, and the
electrode 3 is deposited on the magnetic film 2. Nevertheless, the positional relationship
between the magnetic film 2 and the electrode 3 is not limited to the above embodiments. For jj
j.
example, an electrode 2 may be first deposited on a substrate 4, and a magnetic film 2 may be
deposited on the electrode 2. In such a case, it is also possible to implement a thermoelectric
15 converter element having the same function. This process, which deposits a thin electrode on a
flat substrate, may be more advantageous in some implementation methods.
Furthermore, this application is based upon and claims the benefit of priority from |
if.
Japanese patent application No. 2010-025797, filed on February 9, 2010, and Japanese patent
f
application No. 2011-192874, filed on September 5, 2011, the disclosure of which is
r
20 incorporated herein in its entirety by reference. i
Description of the Reference Numerals and Signs:
1 thermoelectric converter element
la thermoelectric converter element
25 lb thermoelectric converter element [.
i
2 magnetic film
3 electrode
4 substrate j
5 power generation portion 30 7 terminal
9 terminal
•
11 temperature gradient application portion
13 magnetization portion
36
£ CLAIMS
1. A thermoelectric converter element characterized by comprising:
a substrate;
5 a magnetic film provided on the substrate with a certain magnetization direction and
formed of a polycrystalline magnetically insulating material; and
an electrode provided on the magnetic film with a material exhibiting a spin-orbit
interaction.
10 2. The thermoelectric converter element as recited in claim 1, characterized by being
configured so that, when a temperature gradient is applied to the magnetic film, a spin current is
generated so as to flow from the magnetic film toward the electrode, and a current is generated in
a direction perpendicular to the magnetization direction of the magnetic film by an inverse spin
Hall effect of the electrode.
15
3. The thermoelectric converter element as recited in claim 1 or 2, characterized by
comprising a thermoelectromotive force output portion provided at two points on the electrode
for outputting a thermoelectromotive force generated by the current as a potential difference
between the two points.
20
4. The thermoelectric converter element as recited in any one of claims 1 to 3,
characterized in that the magnetization direction has a component in parallel to a film surface of
the magnetic film, and a spin current is generated so as to flow toward the electrode when a
temperature gradient perpendicular to a surface direction is applied to the magnetic film.
25
5. The thermoelectric converter element as recited in any one of claims 1 to 4,
characterized by comprising a temperature gradient application portion for applying a
temperature gradient to the magnetic film.
30 6. The thermoelectric converter element as recited in any one of claims 1 to 5,
characterized in that the magnetic film has a film thickness between tJS and 5tc where tc is a
characteristic thickness at which a thermoelectromotive force generated by the current is
saturated with respect to an increase of a film thickness of the magnetic film.
37
| ^ 7. The thermoelectric converter element as recited in any one of claims 1 to 6,
characterized in that the magnetic film has a film thickness that is not more than 1/10 of a film
thickness of the substrate.
5 8. The thermoelectric converter element as recited in any one of claims 1 to 7,
characterized by comprising a magnetization portion for magnetizing the magnetic film in the
magnetization direction.
9. The thermoelectric converter element as recited in any one of claims 1 to 8,
10 characterized in that the magnetic film has coercivity to cause spontaneous magnetization in the
magnetization direction.
10. The thermoelectric converter element as recited in any one of claims 1 to 9,
characterized in that the magnetic film is formed of a material including yttrium iron garnet.
15
11. The thermoelectric converter element as recited in any one of claims 1 to 10,
characterized in that the magnetic film is formed of a material in which an impurity is substituted
for part of an yttrium site of yttrium iron garnet.
20 12. The thermoelectric converter element as recited in any one of claims 1 to 10,
characterized in that the magnetic film comprises yttrium iron garnet doped with Bi.
13. The thermoelectric converter element as recited in claim 12, characterized in that the
magnetic film comprises yttrium iron garnet doped with Bi that has a composition of
25 BixY3-xFe50i2 (0.5 < x < 1.5).
14. The thermoelectric converter element as recited in any one of claims 1 to 13,
characterized in that the magnetic film is formed of a material in which an impurity is substituted
for part of an iron site of yttrium iron garnet so as to have enhanced coercivity.
30
15. The thermoelectric converter element as recited in any one of claims 1 to 14,
characterized in that the magnetic films and the electrodes are alternately stacked.
16. A method of manufacturing a thermoelectric converter element, characterized by
I
j
38
j(J^ying a solution containing a magnetic material on a substrate, heating the substrate to sinter
the magnetic material, and depositing an electrode on the magnetic material so as to produce the
thermoelectric converter element as recited in any one of claims 1 to 15.
5 17. A method of manufacturing a thermoelectric converter element, characterized by
blowing particles containing a magnetic material onto a substrate by an aerosol deposition
method to form a magnetic film and depositing an electrode on the magnetic film so as to
produce the thermoelectric converter element as recited in any one of claims 1 to 15.
10 18. A thermoelectric conversion method characterized by applying a temperature
gradient to the magnetic film of the thermoelectric converter element as recited in any one of
claims 1 to 15 to generate a spin current flowing from the magnetic film toward the electrode and
generating a current in the direction perpendicular to the magnetization direction of the magnetic
film by an inverse spin Hall effect in the electrode.
15
19. A thermoelectric conversion method characterized by applying a temperature
difference while using, for a low-temperature side, a side of the substrate of the thermoelectric
converter element as recited in any one of claims 1 to 15 on which the magnetic film is provided
and using another side of the substrate for a high-temperature side.