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The mechanical properties of as-sintered and heat-exposed polycrystalline Mg2Si were investigated. The strength of the as-fabricated specimen depends on the surface flaws. After heat exposure in Ar atmosphere, oxidized products formed, mainly consisting of MgO. The strength increased after the heat exposure, and the surface oxidation product filled the surface cracks. After the surface oxidation products were removed, the strength and TE properties were the same as those of the as-fabricated specimens.
The magnesium compound Mg2Si and its solid solutions are expected as n-type thermoelectric (TE) material because they are non-toxic, have a large Clarke number, and are light weight. In this study, we improved TE performance by doping Ge into Sb-doped Mg2Si to cause phonon scattering and increase carrier concentration. A bulk of Sb-doped Si-Ge alloy as the raw material was fabricated using an arc-melting method. A high-purity Mg2Si was synthesized from metal Mg and Sb-doped Si-Ge alloy using spark plasma sintering equipment. For the samples with the same Sb concentration, the electrical conductivity was equivalent. On the other hand, the Seebeck coefficient was dependent on Ge concentration. Due to phonon scattering, thermal conductivity decreased by a small amount of Ge doping and κph dominated for thermal conduction. The minimum thermal conductivity of Mg2Si0.90Ge0.10 was 2.25 W/mK (κph: 2.06 W/mK, κel: 0.19 W/mK). The dimensionless figure of merit (ZT) for the Mg2Si0.945Ge0.05Sb0.005 sample was higher than that of the others due to reducing thermal conductivity and increasing carrier concentration. The maximum ZT was 0.47 at 713 K.
We theoretically investigated the structural and thermoelectric properties of Mg2Si with Al and Sb (Na and B) as n-type (p-type) impurities. Supercell calculations involving relaxation of the atomic positions using an ab initio pseudo-potential method were performed. The formation energies, Eform,i, for the i = Mg, Si, and 4b sites, and consequently, the energetically preferred sites occupied by the impurities, were discussed. The calculated Eform,i were used to estimate the impurity-site occupancy probabilities, pi(T), based on the canonical distribution in the equilibrium state, i.e., pi(T) ∝ exp(−Eform,i/kBT) (Boltzmann constant: kB, temperature: T), and the resultant effects on the carrier concentration. Next, an all-electron full-potential linearized augmented-plane-wave calculation was performed based on the optimized structures, and the temperature dependence of the thermoelectromotive force (the Seebeck coefficient) was evaluated using the Boltzmann transport equation. The calculated and experimental results for n-type doped systems were compared.
In this study, we fabricated Mg2Si from metal Mg and Si with different particle sizes (425 - 300, 300 - 180, and 75 μm or less) using spark plasma sintering (SPS) equipment. Additionally, the Mg2Si formation was investigated. A sieved Si powder was mixed with metal Mg powder in an inert gas (Ar) atmosphere. The mixture was placed in a graphite die while still in an Ar atmosphere and subjected to SPS at 923 K and 1113 K. The obtained sintering bodies were Mg2Si particles with a size of about 5 μm. Then, the sintered bodies were evaluated by X-ray diffraction (XRD). As a result, it was confirmed that generation of Mg2Si increased with decreasing Si particle size.
Magnesium silicide (Mg2Si) has attracted much interest as an n-type thermoelectric material because it is eco-friendly, non-toxic, light, and relatively abundant compared with other thermoelectric materials. In this study, we tried to improve the thermoelectric performance by doping Sb and Ge in the Mg2Si, as well as further optimizing x in the carrier concentration to cause phonon scattering. A high purity Mg2Si was synthesized from metal Mg and Sb doped Si-Ge alloy by using spark plasma sintering (SPS) equipment. The sintered samples were cut and polished. They were evaluated by using X-ray diffraction (XRD) and X-ray fluorescence (XRF) analyses. The carrier concentration of the samples was measured by using Hall measurement equipment. The electrical conductivity and Seebeck coefficient were measured by using a standard four-probe method in a He atmosphere. The thermal conductivity was measured by using a laser-flash system. We succeeded in obtaining a Sb doped Mg2Si0.95Ge0.05 sintered body easily without any impurities with the SPS equipment. The electrical conductivity of the sample was increased, and thermal conductivity was decreased by increasing the amount of doped Sb. The dimensionless figure of merit ZT became 0.74 at 733 K in the Mg2Si0.95-xGe0.05Sbx sample with x = 0.0022.
Mg2Si bulk was fabricated by spark plasma sintering (SPS) nano-powder, and the thermoelectric characteristics of the bulk sample were evaluated at temperatures up to 873 K. A pre-synthesized all-molten commercial polycrystalline Mg2Si source (un-doped n-type semiconductor) was pulverized into powder of 75 μm or less. To obtain nano-sized fine powder, the powder was milled using planetary ball mill equipment under an inert atmosphere. Fine Mg2Si nano-powder with a mean grain size of about 500 nm was obtained. XRD analysis confirmed that no MgO existed in the nano-powder. The fine powder was put in a graphite die to obtain a sintering body of Mg2Si and treated by SPS under vacuum conditions. The resulting Mg2Si bulk had high density and did not crack. However, the XRD analysis revealed a small amount of MgO in it. The thermoelectric properties (electrical conductivity, Seebeck coefficient, and thermal conductivity) were measured from room temperature to 873 K. The microstructure of the sintered body was observed by scanning electron microscopy. The maximum dimensionless figure of merit of a sample made from Mg2Si nano-powder was ZT = 0.67 at 873 K.
Thermoelectric power generation has been attracting attention as a technology for waste heat utilization in which thermal energy is directly converted into electric energy. It is well known that layered cobalt oxide compounds such as NaCo2O4 and Ca3Co4O9 have high thermoelectric properties in p-type oxide semiconductors. However, in most cases, the thermoelectric properties in n-type oxide materials are not as high. Therefore, n-type magnesium silicide (Mg2Si) has been studied as an alternative due to its non-toxicity, environmental friendliness, lightweight property, and comparative abundance compared with other TE systems. In this study, we fabricated π-structure thermoelectric power generation devices using p-type NaCo2O4 elements and n-type Mg2Si elements. The p- and n-type sintering bodies were fabricated by spark plasma sintering (SPS). To reduce the resistance at the interface between elements and electrodes, we processed the surface of the elements before fabricating the devices. The end face of a Mg2Si element was covered with Ni by SPS and that of a NaCo2O4 element was coated with Ag by silver paste and soldering.
The thermoelectric device consisted of 18 pairs of p-type and n-type legs connected with Ag electrodes. The cross-sectional and thickness dimensions of the p-type elements were 3.0 mm × 5.0 mm × 7.6 mm (t) and those of the n-type elements were 3.0 mm × 3.0 mm × 7.6 mm (t). The open circuit voltage was 1.9 V and the maximum output power was 1.4 W at a heat source temperature of 873 K and a cooling water temperature of 283 K in air.
The thermoelectrical properties of α and γ phases of NaxCo2O4 having different amounts of Na were evaluated. The γ NaxCo2O4 samples were synthesized by thermal decomposition in a metal-citric acid compound, and the α NaxCo2O4 samples were synthesized by self-flux processing. Dense bulk ceramics were fabricated using spark plasma sintering (SPS), and the sintered samples were of high density and highly oriented. The thermoelectrical properties showed that γ NaxCo2O4 had higher electrical conductivity and lower thermal conductivity compared with α NaxCo2O4 and that α NaxCo2O4 had a larger Seebeck coefficient. These results show that γ NaxCo2O4 has a larger power factor and dimensionless figure of merit, ZT, than α NaxCo2O4.
In order to perturb global warming and realize a sustainable global energy system, enhancements in the energy efficiency are required. One of the reliable technologies to reduce the greenhouse gas emissions and the consumption of fossil fuel that is attracting attention is thermoelectric technology, which can directly convert heat into electricity and consequently increase the energy conversion efficiency of power generation by combustion. Magnesium silicide (Mg2Si) has been identified as a promising advanced thermoelectric material operating in the temperature range from 500 to 800 K. Compared with other thermoelectric materials that operate in the same conversion temperature range, such as PbTe, TAGS (Ge-Te-Ag-Sb) and CoSb3, Mg2Si shows promising aspects, such as the abundance of its constituent elements in the earth’s crust and the non-toxicity of its processing by-products, resulting in freedom from care regarding prospective extended restriction on hazardous substances.
Here we have tried to introduce reusing of industrial waste of Si sludge as a source material for Mg2Si, because the current product inversion rate of Si for semiconductor LSI devices remains at 25 to 30 %, while most of the remainder is disposed of as a waste; this is mainly discharged as sludge from grinding and polishing processes. It is possible that the reuse of this waste Si could be effective in both reducing the cost of source Si and in the reduction of industrial waste. On the other hand, recycled materials of standard lightweight magnesium alloys based on the Mg-Al-Zn-Mn system, such as AZ91 or AM50, were also introduced as a Mg source for Mg2Si synthesis. The concept of this work is a production of wasted heat recovery device using environmentally-benign Mg2Si by means of industrial waste or less pure recycled sources.
The efficiency of a thermoelectric device is characterized by the dimensionless figure of merit, ZT=S2σT/κ, of its constituent thermoelectric material, where S is the Seebeck coefficient, σ is the electrical conductivity, κ is the thermal conductivity, and T is the absolute temperature. As a target for practical use, ZT value exceed unity, which gives about 10 % conversion efficiencies, is expected. So far, we succeeded to obtain the Mg2Si with ZT=1.08 using rather pure Si (99.999% : solar grade) and Mg (99.95%) sources. In this article, we report multifarious fabrication processes in order to realize ZT value as high as unity and the detailed thermoelectric properties concerning Mg2Si initiated from reused Si sludge and the recycled Mg-alloy sources. In conjunction, we will also discuss the practical output-power characteristics of the samples with the formation of Ni electrodes by monobloc sintering. A tentative generated power density from the wasted heat at 773 K was ˜2 KW/m2.
Delafossite CuYO2 and Ca doped CuYO2 were prepared by thermal decomposition of a metal-citric acid complex. The starting solution consisted of Cu acetate, Y acetate and Ca acetate as the raw materials. Citric acid was used as the chelating agent, and acetic acid and distilled water were mixed as a solvent. The starting solutions were heated at 723 K for 5 h after drying at 353 K. The obtained powders were amorphous and single phase of orthorhombic Cu2Y2O5 was obtained by heat-treated the amorphous powder at a temperature range between 1073 and 1373 K for 3 h in air. Furthermore, Heat-treating the obtained orthorhombic Cu2Y2O5 at above 1373 K in air caused it to decompose into Y2O3, CuO and Cu2O. On the other hand, the sample powder prepared from a starting solution without citric acid, i.e., single phase of orthorhombic Cu2Y2O5 could not be obtained under the same synthesis conditions as that for a solution with citric acid. We were able to obtain delafossite CuYO2 and Ca doped CuYO2 from orthorhombic Cu2Y2O5 under a low O2 pressure atmosphere at above 1223 K. The obtained delafossite CuYO2 composed hexagonal and rhombohedral phases. The color of the CuYO2 powder was light brown and that of Ca-doped CuYO2 was light green. Diffraction peaks in the XRD pattern were slightly shifted by doping Ca for CuYO2, and these peaks shifted toward to a high diffraction angle with an increasing amount of doped Ca. From these results, we concluded that Ca doped delafossite CuYO2 could be obtained by thermal decomposition of a metal-citric acid complex.
The thermoelectric (TE) properties, such as the Seebeck coefficient, the electrical and thermal conductivities, and the output power, of Sb-doped n-type Mg2Si were studied. A commercial polycrystalline source was used for the source material for the Mg2Si. TE elements with Ni electrodes were fabricated by using a monobloc plasma-activated sintering (PAS) technique. Compared with undoped samples, the ZT values of the Sb-doped samples were higher over the whole temperature range in which measurements were made; the maximum value for the Sb doped Mg2Si was 0.72 at 864 K. The TE characteristics of Sb-doped samples were found to be comparable to those of Bi-doped ones, and no significant difference in ZT value was observed between them. Provisional results showed that the maximum value of the output power was 6.75 mW for the undoped sample, 4.55 mW for a 0.5 at% Sb doped sample, and 5.25 mW for a 1 at% Sb doped sample with ΔT = 500 K (between 873 K and 373 K).
In order to restrain global warming and to realize a sustainable global energy system, further enhancements in energy efficiency are required. One reliable technology for reducing greenhouse gas emissions and the consumption of fossil fuel is thermoelectric technology, which can directly convert heat into electricity and consequently increases the energy conversion efficiency of power generation by combustion. Magnesium silicide (Mg2Si) is a promising candidate for a thermal-to-electric energy-conversion material at operating temperatures ranging from 500 to 800 K. Mg2Si exhibits many promising characteristics, such as the abundance of its constituent elements in the earth’s crust and the non-toxicity of its processing by-products, resulting in freedom from concerns regarding prospective extended restrictions on hazardous substances.
The efficiency of a thermoelectric device is characterized by the dimensionless figure of merit, ZT. It is well known that several kinds of dopants are effective in improving the thermoelectric performance of n-type Mg2Si. With Bi-doped n-type Mg2Si, we have achieved a maximum value of the dimensionless figure-of-merit ZT of ˜1.0 at ˜ 850 K. However, the correlation between the ZT values and the power generation characteristics, which is essential to understand in order to design a structure for a TE power generation module, has not been sufficiently investigated. In order to design a structure for a thermoelectric module using Mg2Si, we examined the correlation between the ZT values and the power-output of a single element using Mg2Si (ZT = 0.6) and Mg2Si doped with donor impurities such as Al and/or Bi (ZT = 0.65˜0.77). The measured single element was 2×2 mm2 in section and 10 mm long. Additionally, we developed and evaluated a new architecture based on a ‘unileg’ structure Mg2Si TE power generation module, which can improve the module lifetime and simplify its manufacture. As a starting material for the fabrication of the single element and the TE modules, pre-synthesized polycrystalline Mg2Si, fabricated by UNION MATERIAL was used. The material was sintered using a plasma-activated sintering (PAS) technique, and, at the same time, Ni electrodes were formed on the Mg2Si by employing of a monobloc PAS technique. The thermoelectric power-outputs were measured under a temperature difference, ΔT, ranging from 100-to-500 K by using UNION MATERIAL UMTE-1000M.
The observed power-output for single element of Mg2Si (ZT = 0.6), 2 at % Bi-doped Mg2Si (ZT = 0.65) and 1at % Bi + 1at % Al-doped Mg2Si (ZT = 0.77) were 23.2 mW, 13.6 mW and 19.4 mW respectively at ΔT = 500 K (between 873 K and 373 K). For the new architecture based on the unileg structure thermoelectric module, the observed value for power-output-per-unit-area was 12 mW/mm2 at ΔT = 500 K.
High electron mobility transistors (HEMTs) with a pseudomorphically strained InAs channel (InAs-PHEMTs) were fabricated, and their high frequency characteristics were estimated by measuring the S-parameters. For a VDS of 1.4 V and VGS of 0.3 V, InAs-PHEMTs showed an excellent intrinsic cut-off frequency (fT, int.) as high as 90 GHz regardless of their longer LG (0.7 μm). Since fT is known to be inversely proportional to LG to the first approximation, fT, int. of our InAs-PHEMTs may reach 630 GHz if their LG is reduced to 0.1 μm.
Moreover, we calculated the InAs-PHEMTs' energy state and potential profile by self-consistently solving the Schrödinger and Poisson equations. In solving the Schrödinger equation, the energy-dependent effective mass was employed to take into account the strong non-parabolicity of InAs conduction-band based on the k·p perturbation theory by E. O. Kane. It was clarified that most electrons are confined to the InAs layer. On the contrary, if the non-parabolicity is not taken into account, electrons will spread over the InGaAs channel layer.
Magnesium silicide (Mg2Si) has been regarded as a candidate for advanced thermoelectric materials which is used in the temperature ranging from 500 to 800 K correspond to that of vehicle exhaust emission. Besides, Mg2Si has benefits such as abundance of constituent element of Mg2Si in the earth's crust and it's non-toxicity substances compared with other thermoelectric materials that operate in the conversion temperature range such as PbTe and CoSb3. The efficiency of a thermoelectric device is characterized by the dimensionless figure of merit, ZT=S2ãT/Û, of its constituent thermoelectric material where S is the Seebeck coefficient, ã is the electrical conductivity, Û is the thermal conductivity, and T is the absolute temperature. For thermoelectric device operation, the use of a material with ZT more than unity is needed to realize a conversion efficiency of ∼10 %. The optimization of doping careers in Mg2Si is required in order to realize unity of ZT. In that way, we have grown Mg2Si crystals along with doping elements of Bi and Al using vertical Bridgman method.
Mg (99.99 %) and Si (99.99999 %) with a stoichiometric Mg : Si ratio of 67 : 33 were mixed congruently and melt into Mg2Si. Prior to the growth, Bi (99.999 %) powder at the ratio from 0.5 to 3 at % for Mg2Si and the pre-synthesized polycrystalline Mg2Si powder were mixed, and Mg2Si crystals were grown at a rate of 3 mm/h by vertical Bridgman method. Grown samples were characterized by x-ray diffraction (XRD) patterns and electron-prove microanalysis (EPMA), and the results indicated that Mg2Si crystals were reproductively grown due to use of polycrystalline Mg2Si as a source material of growth. Hall carrier concentrations were evaluated at room temperature. The electrical conductivity, the Seebeck coefficient, and the thermal conductivity were estimated in the temperature range from RT to 850 K. The grown crystals exhibited n-type conductivity in undoped and all Bi doped conditions. All the Bi doped crystals showed high electrical conductivity and high carrier concentration compared with that of the undoped crystal. On the other hand, the thermal conductivity was lowered in the proportion of the amount of Bi. Consequently, the thermal conductivity for the crystal that was Bi doped at 3 at % was 0.021 W/cmK at 842K, and its ZT reached 0.99 at 842 K, which is near the unity of ZT that is regarded as a standard of practical use for thermoelectric materials. The solid solubility limit of Bi to Mg2Si was assumed to be around 3 at % from our findings, and thus Al was codoped besides Bi in order further to improve the thermoelectric properties. We will discuss the results, additionally.
Polycrystalline Mg2Si was fabricated from a reused-Silicon source, based on Si sludge, using Spark Plasma Sintering technique. The n-type and p-type dopants, bismuth (Bi) and silver (Ag), respectively, were incorporated into the Mg2Si. The thermoelectric properties were estimated from 300 to 873K. The power factors of undoped and Bi-doped samples from the reused-Si source were comparable to those from a solar grade Si source (99.99999%). The power factor was estimated to be 2.5 × 10-5 W/cmK2 for the Bi-doped sample from the reused-Si source. However, the power factor of the Ag-doped, p-type sample from the reused-Si source was lower than that from solar grade Si source. The dimensionless figures of merit of samples from the resused-Si source were slightly lower than those from a solar grade Si source. The dimensionless figure of merit was estimated to be 0.53 at 812 K for Bi-doped sample from the reused-Si source.
Bi2Te3-based thin films were fabricated on glass substrates by the pulsed laser deposition (PLD) method. The vapor pressures of Bi and Te are significantly different, so controlling the stoichiometric composition is difficult when using conventional physical vapor deposition techniques, and the thermoelectric properties of Bi2Te3 films are sensitive to the film composition. PLD is a promising technique for the fabrication of telluride-based films such as Bi2Te3 due to its superior capability for controlling the film composition. Another advantage of PLD is the flexibility that it allows in terms of atmosphere in the reaction chamber; high concentrations of gases such as oxygen or argon can be introduced. We have measured various compositions of Bi2Te3 based films, and have identified the optimal compositions for both n-type and p-type material. The thermal conductivities of these Bi2Te3 films were evaluated by an exact measuring system, and the results were twice as low as those of conventional bulk materials. These results suggest that PLD has significant advantages for the deposition of in-plane Bi2Te3-based thin films.
Si1-xGex alloys show the high power generating efficiency as a thermoelectric- conversion material. We evaluate the thermoelectric power of the n-type SiGe system on the basis of the first principles calculations. The electronic-band-structure calculation is performed using all-electron full-potential linearized augmented-plane-wave (FLAPW) method within the local density approximation (LDA). The Seebeck coefficient is analyzed by the Bloch-Boltzmann equation. We find that the ordered rhombohedral SiGe has high Seebeck coefficient in comparison with zincblende SiGe. The efficiency of the thermoelectric power in Si1-xGex is gained by the local atomic configuration rather than the Ge concentration.
Silver (Ag) doped Mg2Si1-xGex (x=0.1 to 0.4) samples were fabricated using a plasma activated sintering (PAS) method. The doping concentration of Ag was varied from 1 to 5 at.%. Undoped Mg2Si1-xGex exhibits n-type conductivity due to residual impurities in the Mg source material used and unintentionally process-induced impurities. The observed unstable behavior of the Seebeck coefficient of Ag-doped p-type Mg2Si1-xGex (x ≤ 0.3) in the region of 550 to 650 K, exhibiting a considerable drop in the value and occasional conduction type conversion, was correlated with the specific contaminants. For x∼0.4, the observed Seebeck coefficient varied from 0.2 mV/K at 823 K to 0.4 mV/K at room temperature, with no remarkable drop in the value with increasing temperature. An estimated ZT value of 5 at.% Ag doped Mg2Si0.6Ge0.4 was 0.18 at 844 K. It was found that both specific residual impurities and process-induced impurities affected the characteristics of the Seebeck coefficient of Mg2Si1-xGex.
We investigated the Srn+1TinO3n+1 Ruddlesden-Popper homologous series. This material exhibits a wide range of electric behaviors, from a high-dielectric-constant tunable-paraelectric in its undoped form to a metallic superconductor when it is doped with a variety of elements.
The Srn+1TinO3n+1 and the yttrium-doped Srn+1TinO3n+1 Ruddlesden-Popper homologous series were prepared through the thermal decomposition of a metal citric acid complex. The starting solution consisted of the raw materials strontium acetate and titanium alkoxide. Citric acid was used as the chelating agent, and ethanol and distilled water were mixed and used as a solvent. Single phase Sr2TiO4 and Sr3Ti2O7 were produced without creation of SrCO3 by heat-treatment at 1073 and 1473 K, respectively, for three hours. We were unable to produce single phase Sr4Ti3O10. The samples consisted of Sr4Ti3O10 and SrTiO3 phases. Scanning electron microscopy showed that the grain shape of the Sr2TiO4 was plate-like, while those of the Sr3Ti2O7 and Sr4Ti3O10 were not and the grains had large numbers of pores. High-density Sr2-xYxTiO4 (x= 0 to 0.06) ceramic samples were produced under hot-press conditions (1823 K for one hour at a uniaxial pressure of 31.2 MPa). Although the undoped samples were insulators, the yttrium-doped samples showed high electrical conductivity (i.e. that of Sr1.98Y0.02TiO4 was ρ= 8.5×10−5 Ωcm). The Seebeck coefficient of Sr1.98Y0.02TiO4 was –160.7 μV/K, and the thermal conductivity was 3.38 W/mK.
Thermoelectric properties of Sr1-xYxTiO3 (x = 0-0.08) were calculated using a virtual crystal method. Using a Pechini's method, Sr1-xYxTiO3 (x = 0-0.06) precursor powder was prepared. Using this method, we prepared pure SrTiO3 at a lower temperature than would be using the conventional solid-state reaction method. The precursor solution was heated at 823 K for 5 h after drying at 353 K for 8 h to produce the precursor powder. The powder was sintered using a hot pressing technique. The relative densities of ceramics were more than 98%. The Seebeck coefficient and electrical conductivity of the samples were measured using the standard four-probe method in a flowing He gas atmosphere in a temperature range of 323 to 923 K. The conductivities of SrTiO3, Sr0.97Y0.03TiO3, and Sr0.94Y0.06TiO3 at room temperature were 6.61 × 102, 5.61 × 103, and 1.58 × 104 S/m, respectively. The Seebeck coefficients of SrTiO3, Sr0.97Y0.03TiO3, and Sr0.94Y0.06TiO3 at room temperature were -548, -264, and -196 μV/K, respectively.