CN100461479C - Thermoelectric conversion device, and cooling method and power generating method using the device - Google Patents
Thermoelectric conversion device, and cooling method and power generating method using the device Download PDFInfo
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- CN100461479C CN100461479C CNB2004800233129A CN200480023312A CN100461479C CN 100461479 C CN100461479 C CN 100461479C CN B2004800233129 A CNB2004800233129 A CN B2004800233129A CN 200480023312 A CN200480023312 A CN 200480023312A CN 100461479 C CN100461479 C CN 100461479C
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Abstract
A thermoelectric conversion device having a high thermoelectric conversion performance. In the thermoelectric conversion device, electrodes are arranged unlike the arrangements steered by conventional technical knowledge so that current flows in the interlayer direction of a laminar material. A thermoelectric conversion film is epitaxially formed. An electrically conductive layer and an electric insulating layer are alternated. Each electrically conductive layer has an octahedron crystal structure in which a transition metal atom M is positioned at the center and oxygen atoms are positioned at the vertices. The electric insulating layer is made of a metal element or crystalline metal oxide. The c-axis of the laminar material of the electrically conductive layer and electric insulating layer is parallel to the in-plane direction of the base, and the pair of electrodes are arranged so that current flows along the c-axis.
Description
Technical field
The present invention relates to a kind of thermoelectric conversion device that utilizes peltier effect and Seebeck effect that heat energy and electric energy are changed mutually.
Background technology
Seebeck effect (Seebeck effect), even produce the phenomenon of thermo-electromotive force when the two ends of material have temperature difference, according to its temperature difference, thermoelectric power generation is to utilize Seebeck effect heat energy directly to be converted to the technology of electric energy, constitute closed circuit by externally connecing load, can take out electric power.This technology has been applied to off the beaten track with power supply, universe with power supply, military with power supply etc.
Peltier effect (Peltier effect) promptly makes the phenomenon of transfer of heat by the electronics mobile with electric current, thermoelectric-cooled is to utilize the technology of peltier effect.Specifically, the in parallel and connected in electrical series of for example that these two kinds of charge carrier symbols of p N-type semiconductor N and n N-type semiconductor N are different material heat are connected, and when flowing through electric current, utilize the difference of charge carrier symbol to be reflected in the difference of the direction of hot-fluid, are absorbed heat in the junction surface.This technology is as practicability such as the such part cooling of the cooling of the electronic equipment in the space station, wine cooler (wine cooler) etc.
Usually, the performance of thermo-electric converting material is with performance index Z or it be multiply by the nondimensional performance index ZT that absolute temperature T obtains estimate.ZT uses Seebeck coefficient S, electricalresistivity, the pyroconductivity κ of this material, by formula ZT=S
2/ ρ κ represents.In the evaluation according to performance index ZT, thermo-electric converting material in the past can't be said and reach sufficient realistic scale.
Up to the present, a lot of materials are studied as thermo-electric converting material.For example, reported Na as layered oxide
xCoO
2Demonstrate excellent thermoelectric conversion performance (opening flat 9-321346 communique, the international brochure that discloses No. 03/085748) with reference to the spy.In the world discloses No. 03/085748 brochure, as thermoelectric conversion film, the Na that forms on the c face that discloses at sapphire substrates, c axle Surface Vertical orientation, that be c axle and matrix ground is orientated
xCoO
2Film.
Na
xCoO
2Has CoO as the electrical conductivity layer
2Layer and as the structure of the Na layer alternate configurations of electric insulation layer.From above-mentioned expression formula as can be known, in order to improve performance index ZT, the expectation low-resistivity.Therefore, will be with Na
xCoO
2Be the layered oxide of representative during, in the past, mainly carried out drawing the test of the thermoelectric conversion performance on the direction in the face of electrical conductivity layer as thermo-electric converting material.
For layered oxide, attempt to come the resistance of direction in the reduction face by optimizing crystalline orientation.For example, open in the 2000-269560 communique, disclose the sintered body of crystal orientation unanimity the spy.Open the spy and also to disclose polycrystal in the 2003-95741 communique with orientation.
Manufacture method as the material of crystal orientation unanimity proposes: use tabular model (template) make the method for the material of crystalline orientation (with reference to the spy open the 2002-321922 communique, the spy opens the 2002-26407 communique); With sintered body pulverize, heating and melting after the moulding, cooling be with the method (spy opens the 2002-111077 communique) of crystallization; Raw material is dissolved in the solvent, the gel that obtains is fired, make the method (spy opens the 2003-34583 communique) of plate crystal growth etc.
These technology all are the resistivity of coming direction in the reduction face by the orientation that improves layered oxide, and thermoelectric conversion performance is improved.
But, in above-mentioned existing method, present situation is: at the ZT that is limited in as practical standard〉in the material of 1 level, be limited to and in a certain temperature range, only exceed this standard little by little, also be far from reaching extensively to popularize the horizontal ZT as the thermoelectric conversion performance index of target 3.
The communique of open thermoelectric conversion device in the past gathered be recorded in down.
Te Kaiping 9-321346 communique
The spy opens the 2000-269560 communique
The spy opens the 2003-95741 communique
The spy opens the 2002-321922 communique
The spy opens the 2002-26407 communique
The spy opens the 2002-111077 communique
The spy opens the 2003-34583 communique
The spy opens the 2003-133600 communique
The spy opens the 2002-270907 communique
Te Kaiping 11-330569 communique (paragraph sequence number 0002)
The international brochure that discloses No. 03/085748
The spy opens the 2002-316898 communique
The spy opens the 2002-141562 communique
Summary of the invention
The thermoelectric conversion performance of direction even improve its crystalline orientation, also can't reach the desired level of realistic scale in the face of the electrical conductivity layer of bedded substance.
The inventor is direction but also the thermoelectric transfer characteristic of various bedded substances has been carried out wholwe-hearted research repeatedly in the direction (interlayer direction) of electrical conductivity layer and electric insulation layer alternate configurations in the face of electrical conductivity layer not only, found that, the difference of the size of the extra electric field that cause applies, the electrical conductivity layer of bedded substance and the interlayer direction of electric insulation layer unexpectedly demonstrate high thermoelectric conversion performance, thereby finish the present invention.
The invention provides a kind of thermoelectric conversion device, it possesses matrix, be configured in thermoelectric conversion film and pair of electrodes on the above-mentioned matrix, above-mentioned thermoelectric conversion film obtains by epitaxial growth (epitaxialgrowth), and electrical conductivity layer and electric insulation layer alternate configurations, above-mentioned electrical conductivity layer has transition metal atoms M and is positioned at the center, oxygen atom is positioned at the octahedral crystal structure on summit simultaneously, above-mentioned electric insulation layer is made of metallic element simple substance or crystallinity metal oxide, the c axle of the bedded substance that is made of above-mentioned electrical conductivity layer and above-mentioned electric insulation layer is parallel with direction in the face of above-mentioned matrix, and above-mentioned pair of electrodes is configured to make electric current moving along above-mentioned c axial flow.
In addition, the invention provides cooling means and the electricity-generating method that uses this thermoelectric conversion device.Cooling means of the present invention is used above-mentioned thermoelectric conversion device, and electric current is flowed between pair of electrodes, makes thus and produces temperature difference between the pair of electrodes, with any cooling means as low-temp. portion in the pair of electrodes.Electricity-generating method of the present invention uses above-mentioned thermoelectric conversion device, provides heat to make and produces temperature difference between the above-mentioned pair of electrodes, thus, makes and produces potential difference between the pair of electrodes.
According to the present invention, the thermoelectric transfer characteristic of the interlayer direction by utilizing electrical conductivity layer and electric insulation layer alternate configurations obtains than excellent in the past thermoelectric conversion performance in wide temperature range.This superiority is based on the interlayer conduction of bedded substance.
Description of drawings
Fig. 1 is the stereogram of expression based on a kind of mode of thermoelectric conversion device of the present invention.
Fig. 2 is the figure of crystal structure of the thermoelectric conversion film of expression thermoelectric conversion device shown in Figure 1.
Fig. 3 is the stereogram of expression based on the another kind of mode of thermoelectric conversion device of the present invention.
Fig. 4 A is a kind of stereogram of mode that expression has the thermoelectric conversion device of resilient coating, Fig. 4 B is the stereogram of another kind of mode that expression has the thermoelectric conversion device of resilient coating, and Fig. 4 C is the stereogram of another mode of the thermoelectric conversion device of expression with resilient coating.
Fig. 5 is the Na that makes among the expression embodiment 1
0.4CoO
2The X-ray diffraction result's of film figure.
Fig. 6 is the Na that makes among the expression embodiment 1
0.4CoO
2The temperature dependent figure of the resistivity of film.
Fig. 7 is the Na that makes among the expression embodiment 1
0.4CoO
2The temperature dependent figure of the Seebeck coefficient of film.
Fig. 8 A is illustrated among the embodiment 1 epoxy resin is coated on Na
0.4CoO
2The stereogram of the state on the film, Fig. 8 B be make among the expression embodiment 1, with the stereogram of epoxy resin as the thermoelectric conversion device of matrix.
Fig. 9 is the Ca that makes among the expression embodiment 2
0.5CoO
2The X-ray diffraction result's of film figure.
Figure 10 is the Ca that makes among the expression embodiment 2
0.5CoO
2The temperature dependent figure of the resistivity of film.
Figure 11 is the Ca that makes among the expression embodiment 2
0.5CoO
2The temperature dependent figure of the Seebeck coefficient of film.
Figure 12 A be for the structure of the thermoelectric conversion device of representing among the embodiment 3 to make with the stereogram of each inscape exploded representation, Figure 12 B is the stereogram of the thermoelectric conversion device made among the expression embodiment 3.
Figure 13 is the Bi that makes among the expression embodiment 4
2-XPb
XSr
2Co
2O
YThe figure of the crystal structure of monocrystal.
Figure 14 is the Bi that makes among the expression embodiment 4
2-XPb
XSr
2Co
2O
YThe figure of the crystal structure of epitaxial film.
Figure 15 A is the Bi that makes among the expression embodiment 4
1.6Pb
0.4Sr
2Co
2O
YThe X-ray diffraction result's of monocrystal figure, Figure 15 B are the Bi that makes among the expression embodiment 4
2-XPb
XSr
2Co
2O
YThe figure that concerns between the Pb containing ratio X of monocrystal and the c shaft length.
Figure 16 A is the Bi that makes by among the embodiment 4
2Sr
2Co
2O
YThe Laue that monocrystal obtains (Laue) diffraction pattern, Figure 16 B are the Bi that makes by among the embodiment 4
1.8Pb
0.2Sr
2Co
2O
YMonocrystal obtains Laue diffraction figure.
Figure 17 is the Bi that makes among the expression embodiment 4
2Sr
2Co
2O
YThe X-ray diffraction result's of epitaxial film figure.
Figure 18 is the Bi that makes among the expression embodiment 4
1.6Pb
0.4Sr
2Co
2O
YThe temperature dependent figure of the electricalresistivity of monocrystal, Seebeck coefficient S and pyroconductivity κ.
Figure 19 is the Ca that makes among the expression embodiment 5
3Co
4O
9The figure of the crystal structure of epitaxial film.
Figure 20 is the Ca that makes among the expression embodiment 5
3Co
4O
9The X-ray diffraction result's of epitaxial film figure.
Figure 21 is the Ca that makes among the expression embodiment 5
3Co
4O
9The electricalresistivity's of epitaxial film temperature dependent figure.
Embodiment
Below, with reference to the description of drawings embodiments of the present invention.
(execution mode 1)
Thermoelectric conversion device shown in Figure 1 has: panel-shaped base body 11; Thermoelectric conversion film 12 on the matrix 11; With with thermoelectric conversion film 12 contact, be configured in matrix 11 about pair of electrodes 13a, 13b.
The crystal structure of the thermoelectric conversion film 12 of Fig. 2 illustration.Thermoelectric conversion film 12 has the layer structure of electrical conductivity layer 22 and electric insulation layer 23 alternate configurations.That is, thermoelectric conversion film 12 is made of the crystallinity film of electrical conductivity layer 22 and electric insulation layer 23 alternate configurations.
On crystallography, interlayer direction, promptly vertical with aspect direction are called c direction of principal axis 10.Configuration pair of electrodes 13a, 13b make electric current to flow along c direction of principal axis 10.
Electrode 13a, 13b when between these electrodes, applying voltage, electric current gets final product in this direction arranged spaced along the mode that c direction of principal axis 10 flows in thermoelectric conversion film 12, and needn't contact setting with the surface of thermoelectric conversion film 12 as shown in Figure 1.
As shown in Figure 2, thermoelectric conversion film 12 is the crystallinity films with crystal structure of electrical conductivity layer 22 and electric insulation layer 23 alternate configurations.Expectation oxide stratiform material is stable in the air.As the bedded substance of thermoelectric conversion performance excellence, electrical conductivity layer 22 has that transition metal atoms M is positioned at the center, simultaneously oxygen is positioned at octahedron (regular octahedron) crystal structure on summit.Transition metal atoms M is preferably and is selected from least a among following element, particularly Co and the Mn.Electrical conductivity layer 22 contains Co as transition metal atoms M, and from having the CoO of mutually total rib
2The thermoelectric conversion film 12 of octahedral crystal structure obtains excellent thermoelectric conversion performance.MO
2Octahedra mutually altogether rib connect and the structure that constitutes layer is called as CdI
2The type structure.
Has CdI as electrical conductivity layer 22
2The thermoelectric conversion film 12 of type structure can be enumerated and has by formula A
X1MO
Y1The film of the composition of expression.This film be as electric insulation layer 23 the layer A with as electrical conductivity layer 22 the layer MO
Y1The bedded substance of alternate configurations.
At this, A is at least a element that is selected among alkaline-earth metal, Hg, T1, Pb and the Bi such as alkali metal such as Na, K, Li, Ca, Sr, Ba.M is a transition metal, is preferably at least a element that is selected among Co, Ni, Ti, Mn, Fe and the Rh, more preferably is selected from least a among Co and the Mn.In addition, 0.1≤X1≤0.8, preferred 0.2≤X1≤0.8; 1.5≤Y1≤2.5, preferred 1.8≤Y1≤2.2.Elements A and M can be for more than 2 kinds, and for example elements A can be the material that the part of alkali metal and/or alkaline-earth metal is replaced with Hg, T1, Pb, Bi.Y1 is preferred 2, but because Y1 depends on the manufacture method, condition of film etc., so be difficult to it strictly is set at 2.In the following description, be the easy Y1=2 that write as, do not mean that strictness is 2 but write like this.On the other hand, about X1, can adjust artificially to a certain extent.In addition, in following formula, also can consider to replace O (oxygen) with S (silicon) or Se (caesium).
Because metal element A is occupied each position (site) in the crystal at random with the ratio of (X1) * 100%, so frequently cause the scattering of charge carrier (carrier).Therefore, even use the element (metallic element) of monomer as metal as elements A, layer A also has the character of electric insulation.In addition, the layer that is made of metal element A has that transition metal atoms M is positioned at the center, simultaneously the oxygen electrical conductivity layer 22 that is positioned at the octahedral crystal structure on summit is supplied with charge carriers and (had by formula A to having
X1MO
Y1In the film of composition of expression is electronics) effect.Layer with this effect has insulating properties.In this limit, X1 can be 1.0, that is, metal element A can be arranged in all positions of crystal.
In more detail, have by formula A
X1MO
Y1The thermoelectric conversion film 12 of the composition of expression is the MO of 1 to 3 layer of individual layer of one deck (monolayer)
2The alternative stacked body of the electric insulation layer 23 that 1 to the 4 layer of individual layer of electrical conductivity layer 22 and one deck that constitutes constitutes.Existing technology is difficult to make the thermoelectric conversion film 12 of the electric insulation layer 23 of the above thickness of electrical conductivity layer 22 with the above thickness of 4 layers of individual layer or 5 layers of individual layer, but does not get rid of this film among the present invention.
In addition, Fig. 2 represents the crystal structure of each layer individual layer alternate configurations of electrical conductivity layer 22 and electric insulation layer 23.
If apply direct voltage between electrode 13a, 13b, then electric current flows along the c direction of principal axis of thermoelectric conversion film 12, and heat is followed its transmission, and consequently, generation electrode 13a one side draught heat, electrode 13b one are sidelong the phenomenon of heat.If current reversal, then heating and heat release counter-rotating.
When charge carrier is the hole, if with electrode 13a as anodal, with electrode 13b as negative pole, then can produce the phenomenon that electrode 13a one side draught heat, electrode 13b one are sidelong heat.If element M is Ni, then charge carrier has the trend that becomes electronics.In the case, if with electrode 13a as negative pole, with electrode 13b as positive pole, then can produce the phenomenon that electrode 13a one side draught heat, electrode 13b one are sidelong heat.Like this, illustrated device can be used as thermo-electric cooling device.In addition, distinguish in strictness under the situation of electrode 13a and electrode 13b, the former and the latter are designated as " first electrode (reference marks: 13a) " and " second electrode (reference marks: 13b) " respectively.
In the past, in having the thermoelectric conversion film 12 of layer structure, on its c direction of principal axis 10, because resistance is big, Seebeck coefficient is little, so its thermoelectric conversion performance ZT does not enough use.The inventor etc. have successfully produced the bedded substance of interlayer direction (c direction of principal axis 10) along direction in the face by various conditions of research and optimization on matrix 11.And, with this bedded substance as thermoelectric conversion film 12, process that the relation because of the thermoelectric conversion performance that direction was caused of extra electric field is studied in great detail in, discovery can obtain big unexpectedly thermoelectric conversion performance because of the difference of the size of extra electric field on the interlayer direction.
Thinking that one of its reason is the mechanism that hot electron is emitted, under the situation of this bedded substance, is not vacuum but electric insulation layer 23 owing to emit medium, so infer relevant with the mechanism that mixes the complexity that the tunnel conduction effect is arranged.
In same structure, have temperature difference by making between electrode 13a, the 13b, in thermoelectric conversion film 12, charge carrier with heat energy moves between electrode 13a, 13b in order to eliminate temperature difference, the result has electric current to flow.Utilize this effect, can pass through 13a, 13b and take out electric power.Like this, illustrated device can use as thermoelectric generating device.
According to the present invention, the interval of electrode 13a, 13b on the c direction of principal axis 10 of thermoelectric conversion film 12 can freely be set, so can realize returning the few high efficiency device of heat.Thus, the temperature difference of high-temperature portion and low-temp. portion may enlarge.
In order to obtain having structure (with reference to Fig. 2) that each layer 22,23 set up with respect to the Surface Vertical of matrix 11, to be the thermoelectric conversion film 12 that c direction of principal axis 10 becomes the structure of direction in the face, the heating-up temperature of the material of matrix 11 and the matrix 11 when making film is very important.Substrate temperature when using sputtering method is different because of the kind of elements A, but preferred usually in 650～750 ℃ scope.
In addition, about the composition of film, for example,, then can obtain the good film of crystallinity if elements A is set at 0.4≤x≤0.7 when being set at 0.3≤x≤0.5, elements A for Ca when being set at 0.3≤x≤0.6, elements A for Sr during for Na.
The manufacture method of thermoelectric conversion film 12 is not particularly limited, and can use the method based on vapor deposition such as sputtering method, vapour deposition method, laser ablation method, chemical vapor deposition method, perhaps the whole bag of tricks such as growth of liquid phase and solid phase.
As the material of matrix 11, the reasonable sapphire Al of lattice match of preferred substrate 11 and thermoelectric conversion film 12
2O
3, MgO, SrTiO
3, LaAlO
3, NdGaO
3, YAlO
3, LaSrGaO
4, LaSrAlO
4, MgAl
2O
4, ZnO, ZrO
2, TiO
2, Fe
2O
3, Cr
2O
3, single crystal materials such as Si, GaAs.But the crystal face of matrix needs suitably to select.For example, with Na
X1CoO
Y1The film film forming is difficult to make c direction of principal axis 10 to be orientated on the direction in the face of matrix on sapphire C face the time.At this moment, need to select sapphire A face or M face.
On matrix 11, be pre-formed and have the film of c direction of principal axis 10, afterwards, make this film thickening, can obtain thermoelectric conversion film 12 thus by rheotaxial growth process etc. along the structure of direction in the face.According to this method,, can reach more thermoelectric conversion owing to increase at the electric current of interflow or the effective area of hot-fluid.As liquid phase process, for example be layer Na of a axle of vertically setting up orientation
0.5CoO
2During film, with NaCl as flux (flux), mixed C o
3O
4And Na
2CO
3Coccoid, under 1000 ℃, film is dipped into together with matrix in the liquation of fusing, by slowly being cooled to 900 ℃, can obtain the Na about 1mm
0.5CoO
2Thick film.
Based on thermoelectric conversion device of the present invention, in a part that is clamped in the zone between pair of electrodes 13a, the 13b, the thickness of matrix 11 is reduced.The matrix 11 of thin shape structure 31 in the middle of Fig. 3 illustrates and has.
The processing of matrix 11 can be by using ciamond grinder etc. mechanical lapping, chemical etching, ion beam milling etc. (form the face of opposition side of the face of thermoelectric conversion film 12) from the back side of matrix 11 and carry out.By the thin shape structure 31 in the centre of such formation, can suppress mitigation (thermal loss) because of the temperature difference that heat conduction caused is produced by thermoelectric conversion film 12 of matrix 11.Under the very thick situation of thermoelectric conversion film 12, thin shape structure 31 is absorbed in thermoelectric conversion film 12 (with reference to Fig. 4 described later (c)) in the middle of can making.That is, the thickness of matrix 11 can be 0 in the part.As shown in Figure 3, in zone 31, the thickness of matrix 11 is reduced with the cross-section matrix 11 of mode of reporting to the leadship after accomplishing a task with c direction of principal axis 10.
Using matrix that being supported on of thermoelectric conversion film 12 removed the growing substrate front and back carries out all can.For example, Yi Bian can by supporting thermoelectric conversion film 12 this film be separated from growing substrate on one side, also thermoelectric conversion film 12 can be separated the back, it is configured in as on the resin substrate that uses matrix from growing substrate as the resin substrate that uses matrix.
Thermoelectric conversion device of the present invention can also contain the resilient coating that is configured between matrix 11 and the thermoelectric conversion layer 12.
The thermoelectric conversion device that contains resilient coating is shown in Fig. 4 A～Fig. 4 C.At first, epitaxial growth substrate resilient coating 41 on matrix 11, as model, epitaxial growth c direction of principal axis 10 is along the thermoelectric conversion film 12 (Fig. 4 A) of direction in the face with this substrate resilient coating 41.
In the case, but if 41 epitaxial growths of substrate resilient coating, matrix 11 except above-mentioned illustrational substrate, also can use semiconductor substrates such as Si just without limits.As the material of substrate resilient coating 41, for example, can enumerate oxide, metal, specifically, can enumerate to contain and be selected from CeO
2, ZrO
2, TiO
2, ZnO, NiO, Fe
2O
3, Cr
2O
3, Al
2O
3, Cr
2O
3, at least a material among Cr and the Pt.
When using substrate resilient coating 41 to come epitaxial growth thermoelectricity conversion film 12, removing of matrix 11 becomes easily, and the degree of freedom of component structure improves.
Substrate resilient coating 41 also can be applicable to the mode of the thickness of a part that reduces matrix 11.For example, when matrix 11 being ground,, then can carry out high-precision grinding to matrix 11 if be provided with the device that detects the element that constitutes substrate resilient coating 41 by methods such as ion beam millings.Grind by this,, then matrix 11 is cut off (thickness that makes part matrix 11 is 0) and can obtain to keep the thermoelectric conversion device (Fig. 4 B) of the thickness of thermoelectric conversion film 12 if the deep of middle thin shape structure 42 terminates in the substrate resilient coating 41.
Under with the situation of metal film as substrate buffer film 41, by the thin shape structure 42 in centre substrate resilient coating 41 and matrix 11 are cut off simultaneously, can prevent the electric short circuit (Fig. 4 C) of high-temperature portion and low-temp. portion.
Substrate resilient coating 41 can be the multilayer film that two-layer above layer laminate is formed.
More than to have by formula A
X1MO
Y1The thermoelectric conversion film of the composition of expression is that the center is illustrated, but thermoelectric conversion film 12 of the present invention is not limited thereto.
For example, as other electrical conductivity layer 22, can enumerate layer with perovskite structure with octahedral crystal structure that transition metal atoms M is positioned at the center.
Electric insulation layer also can have the rock salt structure.The rock salt structure is made of metallic atom and oxygen atom, for example can have by being selected from formula Sr
2(Bi
2-X4Pb
X4)
2O
4, Ca
2(Co
1-X5Cu
X5)
2O
4, (Ca, Bi)
2CoO
3And Sr
2TiO
3In the composition of at least one expression.At this, 0≤X4≤1,0≤X5≤1.
As another example of thermoelectric conversion film 12, can enumerate and have by formula Bi
2-X2Pb
X2Sr
2Co
2O
Y2The film of the composition of expression.At this, 0≤X2≤0.5,7.5≤Y2≤8.5.As described later, this film has for example CoO
2The laminated construction of electrical conductivity layer and the insulating barrier that constitutes by the rock salt structure of 4 layers of individual layer.
As another example of thermoelectric conversion film 12, can enumerate and have by formula (Ca
1-X3-Y3Sr
X3Bi
Y3)
3Co
4O
9The film of the composition of expression.At this, 0≤X3＜1,0≤Y3≤0.3.As described later, this film has for example CoO
2The laminated construction of electrical conductivity layer and the insulating barrier that constitutes by the rock salt structure of 3 layers of individual layer.
Utilize the rerum natura of the interlayer direction of bedded substance based on thermoelectric conversion element of the present invention, expect that interelectrode distance is long and area electrode is little this moment.The following describes its reason.Actual heat conduction K pyroconductivity κ, element area S
0With length 1 with K=κ S
0/ 1 relation is represented.In thermoelectric conversion device, in order to prevent the mitigation by the temperature difference of peltier effect generation, preferred heat conduction is little.If reduce actual heat conduction, length growth, the area of element are reduced.Therefore, expectation is processed into the elongated shape use with element.In small components such as film, can improve its performance by processing based on photoetching (photolithography) technology etc.
In thermoelectric conversion device of the present invention, because electric current is mobile at the face direction rather than the film thickness direction of thermoelectric conversion film, so guarantee the length 1 of element easily.Under the situation of the epitaxially grown film of mode that vertically is orientated with c axle and matrix surface, the length 1 of element is subjected to the thickness limits of film, is difficult to reach more than the 1mm.Relative therewith, in thermoelectric conversion device of the present invention, the length 1 of element can reach more than the 1mm, is preferably more than the 3mm, more preferably more than the 5mm, is preferably more than the 9mm especially.Specifically, can be on c direction of principal axis 10, the interval predetermined distance is above, the above configuration of for example 1mm pair of electrodes 13a, 13b.
Based on cooling means of the present invention and electricity-generating method, the thermoelectric conversion device that existing method is applied to invent can be implemented.During cooling, best flow pulses electric current between pair of electrodes 13a, 13b.When using pulse current, on one side can suppress caloric value, Yi Bian effectively utilize the high thermoelectric conversion performance that produces by thermoelectric conversion device of the present invention to cool off.Because the hot-fluid of carrying is based on the integrated value of the electric current that flows,, but can suppress the appearance of the Joule heat that produces by resistance when being to use pulse current so even use pulse current, how the amount of hot-fluid also can reduce.
Following according to embodiment, illustrate in greater detail the present invention, but following embodiment is identical with the above, only preferred implementation of the present invention illustrates.
(embodiment 1)
The sapphire Al of, thickness 100 μ ms square at 10mm
2O
3A face substrate on, carry out layered oxide Na
0.4CoO
2Film forming.Film build method is to use the Na of 4 inches of diameters
0.5CoO
2The RF magnetron sputtering of sintered body target plate.
With 80%Ar, 20%O
2Atmosphere remain on 5.0Pa, carry out 1 hour pre-sputter with the power output of 60W after, with pre-sputter the time under the same condition, carry out 5 hours accumulation being heated on 700 ℃ the substrate, thereafter, film on the substrate of heating is cooled off 2 hours to room temperature in oxygen atmosphere, the result obtains the film with metallic luster that thickness is 1000nm.
By energy dispersion type fluorescent X-ray analysis, the ratio of components of Na and Co is approximately Na:Co=0.4:1 in the affirmation film.
With the Na that obtains like this
0.4CoO
2The X-ray diffraction of film is measured the results are shown in Fig. 5.
Except diffraction maximum, also observe the isonomic peak that produces by diffraction from film from sapphire substrate.They are respectively the peaks of (200), (400).
Confirm Na thus
0.4CoO
2Film is with surperficial parallel the mode crystalline orientation and the epitaxial growth of (100) face and substrate.Measure by 4 X-ray diffractions in addition and confirm Na
0.4CoO
2The c axle of crystal in pellicular front, be orientated on the direction.
This Na
0.4CoO
2Film is identical with Fig. 2 to the crystal orientation of substrate.In crystal, can carry out the physical property measurement of both direction with such orientation: the c direction of principal axis with the vertical direction of c axle, the i.e. direction parallel with each layer.
Fig. 6 represents the Na to all directions mensuration
0.4CoO
2The temperature dependency of the resistivity of film.At this, ρ
cFor the c direction of principal axis, be the resistivity of the interlayer direction of each layer.ρ
AbResistivity for the direction parallel with each layer.
Fig. 7 represents Na
0.4CoO
2The temperature dependency of the Seebeck coefficient of film.At this, S
cBe the Seebeck coefficient of interlayer direction, S
AbSeebeck coefficient for the direction parallel with each layer.
Directly accept these results, then following supposition is set up.Promptly infer:,,, can obtain good thermoelectric transfer characteristic so compare with resistivity height, interlayer direction that Seebeck coefficient is little because resistivity is low and Seebeck coefficient is big in the direction parallel with each layer.
In order to study this supposition security in actual use, made thermoelectric conversion device.At first, shown in Fig. 8 A, at thermoelectric conversion film (Na
0.4CoO
2Film) coating epoxy resin and make it to solidify on 12 is as supporter 81.Next, will in containing the closed container of steam, place 30 hours by the laminated body that substrate 11/ thermoelectric conversion film 12/ supporter 81 constitutes.
Its result, hydrone is penetrated into Na
0.4CoO
2The interface of film 12 and sapphire substrate 11, thus, to film stress application, Na
0.4CoO
2Film 12 is peeled off from sapphire substrate 11.
In addition, use sputtering method on c direction of principal axis 10, to keep 9mm mode at interval at thermoelectric conversion film (Na
0.4CoO
2Film) piles up Pt electrode 13a, the 13b of wide 0.5mm, thick 500nm on 12 and surfaces supporter 81 opposition sides.Like this, obtained having the thermoelectric conversion device 82 of the new matrix 81 that constitutes by epoxy resin.
At room temperature, the resistance value between 2 Pt electrode 13a, the 13b is about 100 Ω.When flowing the direct current of 0.1mA consistently between electrode, two ends have about 3 ℃ temperature difference.If the counter-rotating of the flow direction of electric current, then high-temperature portion and low-temp. portion counter-rotating.
Consider Fig. 6 and the axial thermoelectricity capability (ρ of c shown in Figure 7
c, S
c), the effect of the thermal loss that produces by matrix etc., the temperature difference that calculates is below 1 ℃.Therefore, experiment value has reached more than 3 times of inferring according to constant thermoelectricity capability of conversion efficiency.
Usually, thermoelectric conversion performance index ZT has 2 items of Seebeck coefficient, so the physical quantity suitable with Seebeck coefficient is more than 3 times the time, ZT has 1 raising about the order of magnitude.
About guess value and measured value the very big reason that departs from is arranged, (with reference to embodiment 4) analysis is carried out as follows based on Fig. 6 and Fig. 7
(embodiment 2)
Use is by CaO
2, Co
3O
44 inches the raw material target (target) that the sintered body of powder constitutes, under the sputtering condition identical with embodiment 1, the growth thickness is the film of 1000nm on the sapphire M face substrate square at 10mm, that 100 μ m are thick.
By the energy dispersion type x-ray fluorescence analysis, confirm that Ca in this film and the ratio of components of Co are approximately Ca:Co=0.5:1.With this Ca
0.5CoO
2The X-ray diffraction of film is measured the results are shown in Fig. 9.Except the diffraction maximum that produces by sapphire substrate, only observe the index secondary peak of (020) that produces based on diffraction by film.
Confirm Ca thus
0.5CoO
2Film is with the mode epitaxial growth parallel with substrate of (010) face.In addition, measure affirmation, Ca by 4 X-ray diffractions
0.5CoO
2The c axle of crystal in the face of film, be orientated.
Ca after film has just been made
0.5CoO
2Film presents light brown, carries out 2 hours annealing in oxygen atmosphere, under 300 ℃, Ca
0.5CoO
2Film becomes the black with metallic luster.
Figure 10 represents Ca
0.5CoO
2The temperature dependency of the resistance of film.At this, ρ
cBe the resistivity of the interlayer direction of c direction of principal axis, the bedded substance that promptly constitutes by Ca layer and Co layer, ρ
AbResistivity for the direction parallel with each layer.
Figure 11 represents Ca
0.5CoO
2The temperature dependency of the Seebeck coefficient of film.At this, S
cBe the axial Seebeck coefficient of c, S
AbSeebeck coefficient for the direction parallel with each layer.
In addition, with sputtering method with at Ca
0.5CoO
2Keep 9mm mode at interval on film, to pile up the Au electrode of wide 0.5mm, thick 400nm on the c direction of principal axis of film.In addition, the effect of temperature difference by disappearing at once via the heat conduction of substrate in order to alleviate generation as shown in Figure 3, in the zone of cross-section interelectrode wide about 2mm, makes substrate slimming to thickness be about 1 μ m by ion beam milling.
At room temperature, 2 interelectrode resistance values of Au are about 400 Ω.When flowing the electric current of 0.003mA between electrode consistently, two ends have about 2 ℃ temperature difference.The effects of the thermal loss of considering the value of Figure 10 and the axial thermoelectric conversion performance of c shown in Figure 11, being produced by matrix etc., the temperature difference that calculates is 0.1 ℃, so experiment value has reached 20 times of theoretical value.If the actual temperature difference that obtains be scaled thermoelectric conversion performance index ZT then be 400 times.
(embodiment 3)
Use a plurality of thermoelectric conversion devices that obtain by embodiment 1, produce device with bigger effective area.Specifically, shown in Figure 12 A, prepare long 30mm, wide 5mm, 1000 thermoelectric conversion elements 82 of thickness 2mm and absorber plate 121a and the heating panel 121b that constitutes by the square aluminium oxide of 700mm between electrode 13a, the 13b.
Using the material of aluminium oxide as absorber plate 121a and heating panel 121b, is because of pyroconductivity height, uniformity of temperature profile.
Because each thermoelectric conversion element 82 is electrically connected, the surface of absorber plate 121a and heating panel 121b is applied with the high copper of conductance.
Use silver-colored pastel (paste) that electrode 13a, the 13b of thermoelectric conversion device 82 are engaged respectively with the surface with the copper coating of absorber plate 121a and heating panel 121b, obtain the thermoelectric conversion device shown in Figure 12 B.In this device, engage in parallel by electric between the absorber plate 121a of a plurality of thermoelectric conversion devices provided by the invention and the heating panel 121b.This device has about 3 ℃ cooling capacity for the electric power of 1mW.
(embodiment 4)
In the present embodiment, enumerate with Bi
2-X2Pb
X2Sr
2Co
2O
Y2The monocrystal of the layered oxide of the composition formula of (X2=0.4 etc., Y2=7.5～8.5) record and the example of epitaxial film are put down in writing the thermoelectric transfer characteristic of this material.
Bi
2-X2Pb
X2Sr
2Co
2O
yThe monocrystal of (X2=0.4 etc., Y2=7.5～8.5) is made of float-zone method (floating zone method).With Co (NO
3) H
2The precursor of O (precursor) and PbO
2, SrO, BiO mix after forming weighing, makes its temperature rise to 200 ℃ with drying.After the powder that obtains made bead (pellet) shape, sintering was made coccoid in 24 hours again in atmosphere under 1000 ℃.The powder that obtains is pressed into the size of the scale that is suitable for device, if 1150 ℃ of following sintering after about 15 hours in 3 atmospheric oxygen atmospheres crystalline growth, then can obtain having the length 4～6mm of black glossy, the monocrystal of radius 5mm.
Its crystal structure as shown in figure 13.In the present embodiment, in order to make more stabilisation of crystal, use is replaced as the position part of the Bi of the crystal of Figure 13 the material of Pb.Utilize X-ray diffraction to confirm the crystal structure of the material of formation, it be the results are shown in Figure 15 A.Data shown in Figure 15 A are corresponding to the monocrystal of X2=0.4.With the result that analyzes, be Pb containing ratio X (X2) and the relation of the c shaft length of crystal is shown in Figure 15 B.In addition, will be shown in Figure 16 A, Figure 16 B based on the diffraction pattern of Laue phenomenon.
Inductive coupling plasma emission spectrograph) and the composition of EDX (electron dispersive X-rayspectroscopy: electronics the disperses x-ray spectrometer) crystal that affirmation obtains use ICP (inductively coupled plasma emission spectroscopy:.For the amount of the oxygen in the crystal of reality, if make according to composition formula, Y2=8 then, but add than this more oxygen mostly in the reality.The amount of oxygen is difficult to ICP and EDX identification, so Y2 is with expression below 8.5 more than 7.5.
Recorded and narrated Bi to this
2-xPb
xSr
2Co
2O
Y2The manufacture method of the monocrystal of (x=0.4 etc., Y2=7.5～8.5) also can make Bi
2Sr
2Co
2O
y(y=7.5～8.5) epitaxial growth and obtain (Figure 14) on sapphire A face substrate.Specifically, use by BiO, SrO, Co
3O
44 inches the raw material target that the sintered body of coccoid constitutes is with 80%Ar, 20%O
2Atmosphere gas remain on 5.0Pa, carry out 1 hour pre-sputter with the power output of 60W after, under the condition identical, carry out 5 hours accumulation being heated on 700 ℃ the sapphire A face substrate with carrying out pre-sputter.Thereafter, cooling was arrived room temperature in 2 hours in oxygen atmosphere, and can obtain thickness is the film with metallic luster of 1000nm.The data of the X-ray diffraction of the film that obtains are shown in Figure 17.
Then, forward the record of method of measurement and measurement result to, because monocrystal and epitaxial film can obtain roughly the same result, so method of measurement and measurement result during below to monocrystal describe.
Will by the above-mentioned monocrystal that obtains from splitting surface rive and with Surface Machining smooth after, in the both sides of splitting surface with silver-colored pastel installing electrodes and the thermocouple made by nichrome-constantan.Under this state, become the structure that applies electric field, measurement temperature difference to the interlayer direction of electrical conductivity layer and electric insulation layer.This moment, the size of element was 2.0mm * 2.0mm * 0.2mm.Next, the element that electrode has been installed is transferred in the Dewar bottle (dewar), is set to about 2 * 10
-4Under the vacuum of torr.At this moment, in order to prevent any heat leakage sample float is provided with.
Connect power supply and thermometer outside the Dewar bottle respectively, streaming current in the element, the temperature difference of the both sides at measurement Qi Bi interface.The electric current of 10mA if flow between electrode, then the two ends of element reach the temperature difference of about 2K.If the flow direction of electric current changes, then high-temperature portion and low-temp. portion counter-rotating.Even this phenomenon drops to the temperature difference that 50K has 2K similarly with temperature from room temperature.
But, in isolated system (isolated system), during streaming current, the relation of the ST1=K Δ T that represents with Seebeck coefficient S and heat conduction K is arranged between mobile electric current and the temperature difference.The energy that to be expression injected by electric current shows as the expression formula of temperature difference by pyroconductivity, also is the basic representation of the mensuration that is called as the Harman method when measuring pyroconductivity.At this, the area S of heat conduction K enough pyroconductivity κ of energy and element
0And length 1, as mentioned above, be expressed as K=κ S
0/ 1.
Till now, with the Bi that obtains
1.6Pb
0.4Sr
2Co
2O
Y2The electricalresistivity of all directions in (Y2=7.5～8.5), Seebeck coefficient S and pyroconductivity κ are shown in Figure 18.The value of Seebeck coefficient S and the pyroconductivity κ value that the method that is called as steady state method is measured of all serving as reasons, be under thermal equilibrium state, the both sides of element have the temperature difference of about 0.1K, measure thermo-electromotive force and the resulting value of temperature difference.
The result of the steady state method of room temperature shows, uses κ～5mW/cmK and S～100 μ V/K, and the temperature difference of being estimated by relational expression ST1=K Δ T is Δ T～0.06K, and the measured value in the present embodiment demonstrates the temperature difference bigger about 30 times than this estimated value.
This is because have temperature difference about 0.1K, when measuring thermo-electromotive force and temperature difference, be subjected to the voltage about 10 μ V on the element, and approximately be subjected to the voltage of 0.5mV when flowing through the electric current of 10mA.That is to say that the measurement of flowing through in the embodiments of the invention of electric current is compared with the measurement in the common steady state method, is that system is applied the measurement of carrying out after the very large disturbance.Can think, because the electric current that applies in the present embodiment has surmounted the potential barrier of unsurpassable electrical conductivity layer and insulating barrier in steady state method, so observed thermoelectric conversion effect by tunnel current that surpasses common electrical conductivity effect and the generation of electronic emission effect.
In the present embodiment, S/K can obtain the about 30 times value according to the measurement result of steady state method, and thinks that heat conduction K narrows down to about 1/30 and compares, still think Seebeck coefficient S increase about 30 times more natural.When considering that in performance index this is as a result, performance index ZT=S
2/ ρ κ increases about 900 times with comparing according to the mensuration of steady state method.
Like this, the thermoelectric transfer characteristic of the interlayer direction of the bedded substance that electrical conductivity layer and electric insulation layer are alternately arranged, with under common thermal equilibrium state, compared by the resulting thermoelectric conversion performance of the steady state method of measuring based on small temperature difference, performance index ZT becomes about 900 times size.
With the above embodiments form sharp contrast be, for the thermoelectric conversion performance of direction in the face of electrical conductivity layer, by under thermal equilibrium state, have the data that Harman method that data that the steady state method of small temperature difference obtains measure with flowing through electric current like that by present embodiment obtains and demonstrate fabulous consistency.
In other words, because the difference of the thermoelectric transfer characteristic that the difference of the size of disturbance causes is the distinctive phenomenon of interlayer direction, the new effect by tunnel current and electronic emission phenomenon is appreciated that.Because this effect, the thermoelectric transfer characteristic of the interlayer direction of electrical conductivity layer and electric insulation layer is compared with the thermoelectric conversion performance that is obtained by steady state method, performance index ZT becomes about 900 times size, realizes being equivalent to ZT in the wide temperature range between the 800K at 50K〉1 high-performance.
(embodiment 5)
In the present embodiment, be documented in epitaxially grown Ca on the matrix
3Co
4O
9Thermoelectricity capability.
Figure 19 represents in the present embodiment epitaxial growth Ca on matrix 11
3Co
4O
9Film.Ca
3Co
4O
9Has CoO as electrical conductivity layer 22
2The layer, as electric insulation layer 23 by formula Ca
2CoO
33 layers of rock salt structure of expression.The a direction of principal axis 20 of the crystal of this film and the Surface Vertical of matrix 11 (in other words, crystal a axle orientation), c direction of principal axis 10 is along direction in the face.As matrix, use sapphire Al
2O
3A face substrate.
This film uses by Co
3O
4, CaO
24 inches raw material target constituting of the sintered body of coccoid, with 80%Ar, 20%O
2Atmosphere remain on 5.0Pa, carry out 1 hour pre-sputter with the power output of 60W after, under the condition identical with pre-sputter, be heated on 700 ℃ the substrate and carrying out 5 hours accumulation.Thereafter, cooling was arrived room temperature in 2 hours in oxygen atmosphere, and obtaining thickness is the film with metallic luster of 1000nm.
With the Ca that obtains like this
3Co
4O
9The X-ray diffraction of film is measured the results are shown in Figure 20.Except diffraction maximum, also observe the isonomic peak that produces by diffraction from film from sapphire substrate.They are respectively the peaks of (110), (220).Confirm Ca thus
3Co
4O
9Film is with (110) face mode crystalline orientation and the growth parallel with substrate.In addition, show Ca by 4 X-ray diffractions mensuration
3Co
4O
9The c axle of crystal in pellicular front, be orientated.
If obtain crystal orientation shown in Figure 19, then can carry out 2 physical property measurements in opposite directions: c direction of principal axis and the direction vertical, promptly and CoO with the c axle
2The direction that layer is parallel.
Figure 21 is illustrated in all directions and measures the Ca that obtains
3Co
4O
9The temperature dependency of the resistivity of film.At this, ρ
cBe the resistivity of c direction of principal axis, interlayer direction, ρ
AbResistivity for the direction parallel with each layer.
On the above-mentioned element that obtains, utilize sputtering method, with at Ca
0.5CoO
2Keep 9mm mode at interval on this film, to pile up the Au electrode of wide 0.5mm, thick 400nm on the c direction of principal axis of film.In addition, for the temperature difference that the alleviates generation effect by disappearing at once via the heat conduction of substrate, the matrix slimming of part that makes interelectrode wide about 2mm by ion beam milling is to the about 1 μ m of thickness, thus in the middle of matrix part is provided with shape structure carefully.
At room temperature, the resistance value between two Au electrodes is about 400 Ω.When flowing the electric current of 0.003mA between the electrode consistently, two ends have the temperature difference of about 1K.Consider that the temperature difference that the effect etc. of axial resistance of c and Seebeck coefficient, other thermal loss that is produced by matrix calculates is 0.1K, experiment value is 10 times of theoretical value.If it is scaled thermoelectric conversion performance index ZT, then increase about 100 times with comparing according to the mensuration of steady state method.As can be known, in the case, in the wide temperature range between the 800K, will realize being equivalent to ZT at 50K〉1 high-performance.
Utilizability on the industry
According to the present invention, utilize the effect (pyroelectric effect) that surmounts common electrical conductivity phenomenon Tunnel current and thermionic emission phenomenon, can provide to have in the past can't imagine high thermoelectric The thermoelectric conversion device of conversion performance. In the making of this device, take photoetching process as representative with The technology that past thin-film component forms also can be suitable for. Because this device is freely guaranteed electricity easily The distance of interpolar is longer, so be easy to realize high efficiency. Thus, the present invention changes at thermoelectricity Having very high industrial utilization in the field of device is worth.
Claims (24)
1. thermoelectric conversion device is characterized in that:
Possess matrix, be configured in thermoelectric conversion film and pair of electrodes on the described matrix,
Described thermoelectric conversion film obtains by epitaxial growth, and is the crystallinity film that is formed by electrical conductivity layer and electric insulation layer alternate configurations,
Described electrical conductivity layer has that transition metal atoms M is positioned at the center, simultaneously oxygen atom is positioned at the octahedral crystal structure on summit,
Described electric insulation layer is made of metallic element or crystallinity metal oxide,
The c axle of the described crystallinity film that is formed by described electrical conductivity layer and described electric insulation layer is parallel with direction in the face of described matrix,
Described pair of electrodes is configured to make electric current moving along described c axial flow.
2. thermoelectric conversion device as claimed in claim 1 is characterized in that:
Described transition metal atoms M is selected from least a among Co and the Mn.
3. thermoelectric conversion device as claimed in claim 2 is characterized in that:
Described electrical conductivity layer contains Co as described transition metal atoms M, and has the CoO of mutually total rib
2The octahedral crystal structure.
4. thermoelectric conversion device as claimed in claim 1 is characterized in that:
Described electric insulation layer is made of metallic element.
5. thermoelectric conversion device as claimed in claim 4 is characterized in that:
Described metallic element is to be selected from least a among alkali metal, alkaline-earth metal, Hg, Tl, Pb and the Bi.
6. thermoelectric conversion device as claimed in claim 4 is characterized in that:
Described electric insulation layer is made of 1～3 layer individual layer.
7. thermoelectric conversion device as claimed in claim 1 is characterized in that:
Described electric insulation layer is made of the crystallinity metal oxide.
8. thermoelectric conversion device as claimed in claim 7 is characterized in that:
Described electric insulation layer is made of 1～4 layer individual layer.
9. thermoelectric conversion device as claimed in claim 7 is characterized in that:
Described electric insulation layer has the rock salt structure.
10. thermoelectric conversion device as claimed in claim 7 is characterized in that:
Described electric insulation layer has by Sr
2(Bi
2-X4Pb
X4)
2O
4, Ca
2(Co
1-X5Cu
X5)
2O
4, (Ca, Bi)
2CoO
3Or Sr
2TiO
3The composition of expression, wherein, 0≤X4≤1,0≤X5≤1.
11. thermoelectric conversion device as claimed in claim 1 is characterized in that:
Described thermoelectric conversion film has by formula A
X1MO
Y1Represented composition,
Wherein, A is at least a element that is selected from alkali metal, alkaline-earth metal, Hg, Tl, Pb and Bi, and M is selected from least a in the transition metal, and X1 is the numerical value below 0.8 more than 0.1, and Y1 is the numerical value below 2.5 more than 1.5.
12. thermoelectric conversion device as claimed in claim 11 is characterized in that:
Described M is selected from least a among Co, Ni, Ti, Mn, Fe and the Rh.
13. thermoelectric conversion device as claimed in claim 12 is characterized in that:
Described M is selected from least a among Co and the Mn.
14. thermoelectric conversion device as claimed in claim 1 is characterized in that:
Described thermoelectric conversion film has by formula Bi
2-X2Pb
X2Sr
2Co
2O
Y2Represented composition,
Wherein, X2 is the numerical value below 0.5 more than 0, and Y2 is the numerical value below 8.5 more than 7.5.
15. thermoelectric conversion device as claimed in claim 1 is characterized in that:
Described thermoelectric conversion film has by formula (Ca
1-X3-Y3Sr
X3Bi
Y3)
3Co
4O
9Represented composition,
Wherein, X3 is more than or equal to 0 less than 1 numerical value, and Y3 is the numerical value below 0.3 more than 0, and X3+Y3 is the numerical value below 1 more than 0.
16. thermoelectric conversion device as claimed in claim 1 is characterized in that:
Described electrical conductivity layer contains and is selected from least a among Co and the Mn, and has perovskite structure or CdI
2The type structure,
Described electric insulation layer contains at least a element that is selected among alkali metal, alkaline-earth metal, Hg, Tl, Pb and the Bi, and has the rock salt structure.
17. thermoelectric conversion device as claimed in claim 1 is characterized in that:
On described c direction of principal axis, the above configuration of 1mm at interval of described pair of electrodes.
18. thermoelectric conversion device as claimed in claim 1 is characterized in that:
In a part that is clamped in the zone between the described pair of electrodes, the thickness of matrix reduces.
19. thermoelectric conversion device as claimed in claim 1 is characterized in that:
Also contain the resilient coating that is configured between described matrix and the described thermoelectric conversion film.
20. thermoelectric conversion device as claimed in claim 19 is characterized in that:
Described resilient coating contains and is selected from CeO
2, ZrO
2, TiO
2, ZnO, NiO, Fe
2O
3, Cr
2O
3, Al
2O
3, Cr
2O
3, at least a among Cr and the Pt.
21. thermoelectric conversion device as claimed in claim 1 is characterized in that:
The material of described matrix is a resin.
22. a cooling means is characterized in that:
Use possesses matrix, be configured in the thermoelectric conversion film on the described matrix and the thermoelectric conversion device of pair of electrodes,
By electric current is flowed between described pair of electrodes, make between the described pair of electrodes and produce temperature difference, with in the described pair of electrodes any as low-temp. portion,
Described thermoelectric conversion film obtains by epitaxial growth, and is the crystallinity film that is formed by electrical conductivity layer and electric insulation layer alternate configurations,
Described electrical conductivity layer has that transition metal atoms M is positioned at the center, simultaneously oxygen atom is positioned at the octahedral crystal structure on summit,
Described electric insulation layer is made of metallic element or crystallinity metal oxide,
The c axle of the crystallinity film that is made of described electrical conductivity layer and described electric insulation layer is parallel with direction in the face of described matrix,
Described pair of electrodes is configured to make electric current moving along described c axial flow.
23. cooling means as claimed in claim 22 is characterized in that:
Flow pulses electric current between the described pair of electrodes.
24. an electricity-generating method is characterized in that:
Use possesses matrix, be configured in the thermoelectric conversion film on the described matrix and the thermoelectric conversion device of pair of electrodes,
Provide heat so that produce temperature difference between the described pair of electrodes, make thus between the described pair of electrodes and produce potential difference,
Described thermoelectric conversion film obtains by epitaxial growth, and is the crystallinity film that is formed by electrical conductivity layer and electric insulation layer alternate configurations,
Described electrical conductivity layer has that transition metal atoms M is positioned at the center, simultaneously oxygen atom is positioned at the octahedral crystal structure on summit,
Described electric insulation layer is made of metallic element or crystallinity metal oxide,
The c axle of the crystallinity film that is made of described electrical conductivity layer and described electric insulation layer is parallel with direction in the face of described matrix,
Described pair of electrodes is configured to make electric current moving along described c axial flow.
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| WO2012133314A1 (en) * | 2011-03-28 | 2012-10-04 | 富士フイルム株式会社 | Conductive composition, conductive film using conducive composition, and method for manufacturing conductive film |
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| JP5984748B2 (en) * | 2013-07-01 | 2016-09-06 | 富士フイルム株式会社 | Thermoelectric conversion element and thermoelectric conversion module |
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