Patent Application
20180212131
The present invention relates to a silicon-based thermoelectric conversion material used in a thermoelectric conversion device. cl BACKGROUND
Thermoelectric conversion devices can directly convert thermal energy into electric energy and have no movable member present, in contrast to conventional power generation technologies. For this reason, thermoelectric conversion devices have a lot of merits that they are maintenance-free, have long life and do not generate noise, and further, low-temperature waste heat can be utilized.
The performance of a thermoelectric conversion material is, in general, expressed by the dimensionless figure of merit (ZT). That is, a material having high ZT is a material having high Seebeck coefficient and electric conductivity and having low thermal conductivity.
S: Seebeck coefficient (V/K)
σ: electric conductivity (S/m)
Ke: carrier thermal conductivity (W/m·K)
Kph: lattice thermal conductivity (W/m·K)
T: absolute temperature (T)
The value of the ZT varies depending on the material and the temperature. Bi2Te3 currently used as a thermoelectric conversion material has a dimensionless figure of merit ZT of about 0.8 in a range of relatively low temperatures of 100 to 300° C. The currently used thermoelectric conversion material, however, is mainly composed of Bi, Sb, Te and Pb as rare metals. The deposits of these stocks are small, thus, the material cost thereof is high. Further, these thermoelectric conversion materials have a short life as the device because of tendency of oxidation at high temperatures of 300 to 400° C., and further have a possibility of toxicity.
Accordingly, it has been investigated whether ZT equivalent to the BiTe-based material can be obtained by a Si-based material needing lower cost and having lower toxicity as compared the BiTe-based material. The Si-based material has ZT which is lower remarkably than that of the BiTe-based material since the lattice thermal conductivity of the Si-based material is higher about 100 times in comparison with BiTe. Because of this reason, use of the Si-based material as a thermoelectric conversion material is believed to be difficult. However, it has recently been discovered that the lattice thermal conductivity of a Si-based material generating phonon scattering by nanostructuring of the material can be reduced as compared with a bulk body of the Si-based material. Resultantly, a thermoelectric conversion device using nanostructured Si is drawing attention.
For example, Japanese Patent Application Laid-Open No. H11-317547 discloses a technology for reduction of thermal conductivity and accompanying improvement of the property (thermoelectric figure of merit) of a thermoelectric conversion device, by introducing a lot of very fine vacancies dispersed at an interval equivalent to or smaller than the mean free path of electrons and phonons into the semiconductor material. Further, it is also possible to improve the thermoelectric performance by filling another semiconductor or a metal into fine vacancies. As the method of forming the fine vacancies, an electrochemical reaction (for example, anodic reaction) is used, and for filling another semiconductor or a metal, a method of immersing into a melted semiconductor or metal is used.
In Benjamin. M. C. et al., Nano let. 13(2013) 5503, nanostructuring of Si by means of top down using electron beam lithography is tried, and a method of forming a thermoelectric conversion device having a structure consisting of a Si nanowire having a diameter of tens of nm and SiO2 coating the outer peripheral part thereof is disclosed.
In addition, International Publication WO2012/173162 discloses a method of forming a quantum dot by a bio-template technology and a neutral particle beam etching technology. As development of its use, a solar battery and laser are described. As the quantum dot to be formed, Si and GaAs are disclosed, and as the embedding material, SiC, SiO2, (Si3N4) and the like are disclosed.
In the method of the invention described in Japanese Patent Application Laid-Open No. H11-317547, a silicon substrate is made into porous and an effect of reducing thermal conductivity can be expected, however, lowering of Seebeck coefficient due to lowering of electron mobility becomes remarkable simultaneously. Though it is necessary to control pore diameter, density and the like for this reason, they cannot be controlled easily by disclosed means (such as anodization) and the improvement of the thermoelectric property is limited. There is also disclosed a method of filling a BiTe-based material into pores (vacancies) as the means for improving ZT, however, it is difficult to fill a material having melting point equivalent to that of a silicon substrate forming pores into the pore. Therefore, the method of the invention described in Japanese Patent Application Laid-Open No. H11-317547 cannot solve the problem of use of rare metals.
The method described in Benjamin. M. C. et al., Nano let. 13(2013) 5503 uses a means combining a current lithography technology (electron beam lithography) and top down (ICP plasma etching). By this means, control of pore diameter and density which is the problem in Japanese Patent Application Laid-Open No. H11-317547 is made possible. However, there is a problem that it is difficult to form a structure having a size of 20 nm or less, such a structure being believed to be necessary for reducing the lattice thermal conductivity of silicon, since formation of a nanostructure having a size of about tens of nm is boundary according to the current lithography technology.
Further, the two-dimensional quantum nanodot array using a material of a quantum dot and an embedding material described in International Publication WO2012/173162 cannot manifest an excellent thermoelectric conversion performance since a difference in energy between the valence bands or the conduction bands of SiC and SiN disclosed as the embedding material with respect to Si used as the dot formation material (namely, a different in energy between the valence band of the dot formation material and the valence band of the embedding material, or a difference in energy between the conduction band of the dot formation material and the conduction band of the embedding material) is large. Group III-V semiconductors such as GaAs have a problem of high toxicity.
The present invention is made for solving the problems of conventional technologies as described above, and has an object of obtaining a thermoelectric conversion material manifesting an excellent thermoelectric conversion performance, using a silicon-based material.
The present inventors have intensively studied and resultantly found that a high performance thermoelectric conversion material using a silicon-based material is obtained by processing the silicon-based material into nanodots having a size of 20 nm or less and by filling the embedding material between the dots, wherein either one or both of a difference in energy between the valence band of the silicon-based material constituting the nanodot and the valence band of the embedding material and a difference in energy between the conduction band of the silicon-based material constituting the nanodot and the conduction band of the embedding material are in the range of 0.1 eV or more and 0.3 eV or less, leading to completion of the present invention.
Specifically, the present invention provides the followings.
A thermoelectric conversion material characterized in that columnar or spherical nanodots having a diameter of 20 nm or less are embedded in an embedding layer at an area density of 5×1010/cm2 or more and an interval between the nanodots of 0.5 nm or more and 30.0 nm or less, and the first material constituting the nanodot is a material containing silicon in an amount of 30 atom % or more, and, either one or both of a difference in energy between the valence band of the first material and the valence band of the second material constituting the embedding layer and a difference in energy between the conduction band of the first material and the conduction band of the second material constituting the embedding layer are in the range of 0.1 eV or more and 0.3 eV or less.
The thermoelectric conversion material according to Invention 1, characterized in that the first material is silicon, and the second material is silicongermanium in which the molar ratio of silicon to germanium is 20:80 to 80:20.
A production method of the thermoelectric conversion material according to Invention 1, characterized by comprising a step of arraying nanoparticles having a diameter of 1 nm or more and 20 nm or less on a semiconductor layer, a step of forming a columnar or spherical nanodot having a diameter of 20 nm or less by etching the semiconductor layer utilizing the nanoparticles as a mask, and a step of forming an embedding layer so as to embed the nanodot.
The production method of the thermoelectric conversion material according to Invention 3, characterized in that the nanoparticle is at least one selected from the group consisting of a polystyrene particle, a latex particle and a self-assembled polymer.
The production method of the thermoelectric conversion material according to Invention 3, characterized in that the nanoparticle is at least one selected from the group consisting of a silica particle and a metal compound particle.
A production method of the thermoelectric conversion material according to Claim 1, characterized by comprising a step of arraying protein particles containing a metal on a semiconductor layer, a step of forming a metal compound particle by removing a protein from the protein particle, a step of forming a columnar or spherical nanodot having a diameter of 20 nm or less by etching the semiconductor layer utilizing the metal compound particles as a mask, a step of removing the metal compound particles, and a step of forming an embedding layer so as to embed the nanodot.
The production method of the thermoelectric conversion material according to Invention 6, characterized in that the protein particle is at least one selected from the group consisting of ferritin and Listeria Dps.
The production method of the thermoelectric conversion material according to Invention 6, characterized in that the surface of the protein particle is modified with a polyethylene glycol chain.
The production method of the thermoelectric conversion material according to any one of Inventions 3 to 8, characterized in that the first material constituting the semiconductor layer is silicon and the second material constituting the embedding layer is silicongermanium in which the molar ratio of silicon to germanium is 20:80 to 80:20.
The present invention will be explained below.
The thermoelectric conversion material of the present invention has a constitution in which columnar or spherical nanodots 1 having a diameter of 20 nm or less are embedded in an embedding layer 3 at an area density of 5×1010/cm2 or more and an interval between the nanodots of 0.5 nm or more and 30.0 nm or less, as shown in
The nanodot has a size of 20 nm or less in which the diameter in the two-dimensional direction in which the embedding layer spreads. When the diameters of the nanodots are measured by an electron microscope and distribution thereof is determined, it is preferable that 90% or more nanodots on a number basis are included in the range of a diameter of 8±5 nm. The nanodot has a thickness of several nm to tens of nm, and may be columnar or spherical, and may also be conical depending on the case.
The interval between the nanodots is 0.5 nm or more and 30.0 nm or less, preferably 0.5 nm or more and 7.0 nm or less. The interval between the nanodots denotes a distance between the outermost surface of a certain nanodot and the outermost surface of the nearest adjacent nanodot.
The area density of the nanodot is determined by the diameter of the nanodot and the interval between the dots, and is 5×1010/cm2 or more, preferably 1×1011/cm2 or more, more preferably 5×1011/cm2 or more and 8×1011/cm2 or less. Regarding the upper limit of the area density, the calculated coverage rate is about 90% in the case of closest-packing (for example, a coverage rate of 90% corresponds to 8.1×1011/cm2 when the dot size is 13 nm.). While one layer of the periodic structure of nanodots is contained in the embedding layer in
By having the periodic structure of nanodots in the embedding layer, phonon scattering occurs at the interface of nanodots and the embedding layer, and it becomes possible to reduce the lattice thermal conductivity of a thermoelectric conversion material.
The first material constituting the nanodot is a material containing silicon in an amount of 30 atom % or more, and a difference in energy between the valence band of the first material and the valence band of the second material constituting the embedding layer or a difference in energy between the conduction band of the first material and the conduction band of the second material constituting the embedding layer is in the range of 0.1 eV or more and 0.3 eV or less.
This makes it possible to form an intermediate band between nanodots and the embedding layer, and there occurs an energy filtering effect in which when carriers accumulated in the embedding layer are transported in the nanodot array, the nanodot array structure constitutes a potential barrier, and low energy carrier components are not transmitted. By this, the spectrum conductivity near the band gap can be controlled, to improve Seebeck coefficient.
It is preferable that the combination of the first material and the second material is a combination of silicon and silicongermanium. By combining these materials, the first material can be etched by neutral particle beam etching without imparting damages, and since the first material and the second material have a suitable difference in the band gap, an intermediate band can be formed between nanodots and the embedding layer. Further, the first material and the second material are each inexpensive and available easily, and a film formation method thereof is also established.
In this constitution, silicon may be monocrystalline silicon or polycrystalline silicon, and may be doped or may not be doped.
Silicongermanium is a semiconductor obtained by adding germanium to silicon, and in the present invention, the content of germanium in silicongermanium is 20 mol % or more and 80 mol % or less, that is, the molar ratio of silicon to germanium is 20:80 to 80:20. The melting point of silicongermanium is 1139-738x+263x2 (x: Si molar concentration, 0.2≤x≤0.8) K, and silicongermanium is known as a thermoelectric conversion material showing high conversion efficiency under high temperature environment (around 600 to 800 K).
The band gap of silicon is 1.1 eV in the case of monocrystal and about 1.5 eV in the case of polycrystal, in contrast, the band gap of silicongermanium (for example, Si0.7Ge0.3) is 1.12−0.41x+0.0008x2 (x: Si molar concentration, 0.2≤x ≤0.8) eV, and when silicon is used as the dot forming material and silicongermanium (for example, Si0.7Ge0.3) is used as the embedding material, band offset of ΔEv=0.26 eV occurs at the valence band side. That is, a difference in energy between the valence band of silicon and the valence band of Si0.7Ge0.3 is 0.26 eV.
The thermoelectric conversion material of the present invention is cheaper, is not restricted in its stock and has lower toxicity as compared with conventional BiTe-based materials since a silicon-based material is used in the thermoelectric conversion material of the present invention. Further, the thermoelectric conversion material of the present invention has excellent thermoelectric figure of merit since a nanostructured silicon-based material is embedded with a prescribed material.
Next, the production process of a thermoelectric conversion material of the present invention will be explained. In the present invention, a semiconductor layer 13 can be etched utilizing the periodic structure of a nanoparticle 9 as a mask, to obtain the periodic structure of a nanodot 1. This will be explained below using figures.
First, nanoparticles 9 are arrayed on a semiconductor layer 13 as shown in
The concentration of the dispersion obtained by dispersing the nanoparticles 9 varies depending on the material of the nanoparticle and the kind of the dispersion medium, and for example, when polystyrene particles are used as the nanoparticles 9, the concentration is preferably in the range of 100 mg/ml to 1 g/ml, and further, more preferably 300 mg/ml to 500 mg/ml. Further, it is also possible to add a salt into the dispersion medium for controlling the Debye length of the nanoparticle. Though the salt to be used is not restricted, it is preferably a salt not containing elements (alkali metals, alkaline earth metals) causing defects as the doping material for a semiconductor.
The application method of the dispersion obtained by dispersing the nanoparticles 9 can be selected from general application methods such as a spin coat method, a Langmuir-Blodgett (LB) method and a cast method.
Thereafter, the semiconductor layer 13 is etched utilizing the periodic structure of the nanoparticles 9 as a mask, to form columnar or spherical nanodots 1, as shown in
In the neutral particle etching apparatus, a plasma chamber generating charged particles is connected to a processing chamber having a stage on which the treatment target is placed. Between the processing chamber and the plasma chamber, a cathode electrode for charge-exchanging positive charged particles to convert them into neutral particles is disposed. The cathode electrode is the carbon aperture and feeds neutral particles to the processing chamber, but blocks UV and VUV generated in the plasma chamber and does not pass them to the processing chamber. The pressure in the plasma chamber is sufficiently larger than the pressure in the processing chamber, and further, the pressure in the processing chamber is such a pressure that the mean free path of a gas is not shorter than the distance between the cathode electrode and the stage.
Thereafter, the nanoparticles 9 having completed the role as a mask are removed as shown in
Thereafter, an embedding layer 3 is formed so as to fill the space between the nanodot 1 and the nanodot 1 as shown in
A film of silicon dioxide, silicon nitride or a metal oxide which is not easily etched as compared with the etching target film may be formed as a protective layer on the semiconductor layer 13, to protect the semiconductor layer 13 and to prevent generation of film defects in etching the semiconductor layer 13.
In the present production method, the periodic structure of the nanodots 1 can be formed at a density of 5×1010/cm2 or more, and further, it becomes possible to fill the space of the periodic structure with a material having melting point equivalent to that of the material constituting the nanodot 1.
As the method of periodically arraying nanoparticles, a method of arraying protein particles containing a metal, then, removing the protein, to obtain metal compound particles can also be used. This method will be explained specifically below.
First, protein particles 11 containing a metal are arrayed on a semiconductor layer 13 as shown in
As the protein particle 11, ferritin as a spherical protein having iron oxide particles having a diameter of 7 nm inside the protein shell having an outer diameter of 13 nm and Listeria Dps having iron oxide particles having a diameter of 5 nm inside the protein shell having an outer diameter of 9 nm can also be used. The surface of the protein particle 11 may be modified with a polyethylene glycol chain, to prevent aggregation of particles and to regulate the interval between particles to attain easy arraying.
For arraying the protein particles 11 on the semiconductor layer 13, a dispersion obtained by dispersing the protein particles 11 in a liquid can be applied on the semiconductor layer 13 to provide uniform arraying.
The concentration of the dispersion obtained by dispersing the protein particles 11 varies depending on the material of the protein particle 11 and the dispersion medium. For example, when ferritin is used as the protein particle 11 and a 40 mM ammonium sulfate aqueous solution is used as the dispersion medium, the ferritin concentration is preferably in the range of 1 mg/ml to 500 mg/ml, and further, more preferably 1 mg/ml to 50 mg/ml. The dispersion medium for the protein particle 11 can be appropriately selected, and for example, water, a water-alcohol mixed liquid and an organic solvent can be used. Further, it is also possible to add a salt into the dispersion medium for controlling the Debye length of the nanoparticle. Though the salt to be used is not restricted, it is preferably a salt not containing elements (alkali metals, alkaline earth metals) causing defects as the doping material for a semiconductor.
Subsequently, the protein is removed from the protein particle 11, to expose the metal compound particle, as shown in
Further, the semiconductor layer 13 is etched utilizing the periodic metal compound particles 15 as a mask, to form columnar or spherical nanodots 1 having a diameter of 20 nm or less having the periodic structure, as shown in
Thereafter, the metal compound particles 15 having completed the role as a mask are removed as shown in
Further, the embedding layer 3 is formed so as to fill the space between the nanodot 1 and the nanodot 1, as shown in
The present invention will be further explained referring to examples and comparative examples.
(a) On a Si substrate with an oxidized film, amorphous Si having a thickness of 10 nm was deposited by an electron beam deposition method. Next, it was annealed in a nitrogen atmosphere, to obtain polymerized Si.
(b) The polymerized Si was oxidized by a neutral particle beam apparatus, and a surface oxidized film (SiO2) having a thickness of 3.8 nm was deposited thereon.
(c) Next, a dispersion obtained by dispersing ferritin (dispersion medium: 40 mM ammonium sulfate aqueous solution, ferritin concentration: 2.5 mg/ml) was applied on a substrate and dried, to deposit the periodic structure of ferritin on the surface oxidized film (SiO2). pH of the dispersion is preferably about 8 when applied on SiO2, and can be appropriately determined depending on the surface potential of the material to be applied.
(d) The shell of ferritin was removed by annealing at 400° C. in an oxygen atmosphere. On SiO2, the periodic structure in which particulate iron oxide cores are arrayed was deposited. The periodic structure composed of these iron oxide cores is an etching mask in the next step.
(e) First, SiO2 on the surface side was etched utilizing the iron oxide cores as a mask, to remove SiO2 on the surface. Next, polysilicon was removed by neutral particle beam etching utilizing the iron oxide cores as a mask.
(f) The iron oxide cores were removed by wet etching using HCl.
(g) The surface SiO2 layer was removed, then, silicongermanium (Si0.7Ge0.3) having a thickness of 10 nm was deposited on Si nanodots by using MBE.
According to
It is understood from
A thermoelectric conversion material was formed in the same manner as in Example 1, excepting that silicon was used as the first material constituting nanodots and silicon carbide was used as the second material constituting the embedding layer.
Next, the thermoelectric conversion properties of the thermoelectric conversion materials produces in Example 1 and Comparative Example 1 and of only silicon as Comparative Example 2 were measured while changing the measuring temperature. For measurement of thermal conductivity, TCN-2ω (manufactured by ADVANCE RIKO, Inc.) was used, and for electric conductivity and Seebeck coefficient, ZEM-3 (manufactured by ADVANCE RIKO, Inc.) was used.
The thermoelectric conversion properties in examples and comparative examples are shown in
It is understood from comparison of Example 1-1 and Comparative Example 1-1 and Comparative Example 2 or from comparison of Example 1-2 and Comparative Example 1-2 that the thermoelectric conversion material of Example 1 has lowered thermal conductivity and increased electrical conductivity, thus, has higher dimensionless figure of merit, as compared with the thermoelectric conversion material of Comparative Example 1 and the silicon single phase of Comparative Example 2 at the same measurement temperature, as shown in
For the thermoelectric conversion material of Example 1, it is supposed that since silicon is made into a nanodot of 20 nm or less, phonon scattering easily occurs at the nanodot interface, and lattice thermal conductivity which is a seriously problematic in conventional silicon-based thermoelectric conversion devices can be reduced. Further, it is supposed that by filling silicongermanium between nanodots, energy filtering by potential barrier of the periodically arrayed nanodot structure is manifested and a lowering in Seebeck coefficient can be suppressed. That is, it is supposed that a high performance thermoelectric conversion material can be realized by allowing phonon scattering at the silicon nanodot interface and the energy filtering effect by potential barrier by the periodic dot structure to manifest simultaneously.
According to the present invention, it becomes possible to form a high performance thermoelectric conversion material using a silicon-based material, since a lowering in Seebeck coefficient generating in nanostructuring a silicon-based material which is currently problematic is made solvable by the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2015-196414 | Oct 2015 | JP | national |
This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2015-196414, filed on Oct. 2, 2015, and PCT Application No. PCT/JP2016/078191, filed on Sep. 26, 2016, the entire contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2016/078191 | Sep 2016 | US |
| Child | 15934937 | US |
