Su-Dong Park

Lossless hybridization between photovoltaic and thermoelectric devices

The optimal hybridization of photovoltaic (PV) and thermoelectric (TE) devices has long been considered ideal for the efficient harnessing solar energy. Our hybrid approach uses full spectrum solar energy via lossless coupling between PV and TE devices while collecting waste energy from thermalization and transmission losses from PV devices. Achieving lossless coupling makes the power output from the hybrid device equal to the sum of the maximum power outputs produced separately from individual PV and TE devices. TE devices need to have low internal resistances enough to convey photo-generated currents without sacrificing the PV fill factor. Concomitantly, a large number of p-n legs are preferred to drive a high Seebeck voltage in TE. Our simple method of attaching a TE device to a PV device has greatly improved the conversion efficiency and power output of the PV device (~30% at a 15°C temperature gradient across a TE device).

Colloidal synthesis and thermoelectric properties of La-doped SrTiO3 nanoparticles

We describe n-type nanostructured bulk thermoelectric La-doped SrTiO3 materials produced by spark plasma sintering of chemically synthesized colloidal nanocrystals. The La doping levels could be readily controlled from 3 to 9.0 at% by varying the experimental conditions. We found that nanoscale interfaces were preserved even after the sintering process, and the thermoelectric properties of the nanostructured bulk La-doped SrTiO3 were characterized. An enhanced thermoelectric efficiency was observed and attributed to the large decrease in thermal conductivity obtained with no significant change in the Seebeck coefficient or electrical conductivity. The nanostructured bulk of the La-doped SrTiO3 exhibited a maximum ZT of ∼0.37 at 973 K at 9.0 at% La doping, which is one of the highest values reported for doped SrTiO3. Furthermore, the materials showed high thermal stability, which is important for practical high-temperature thermoelectric applications. This report demonstrates the high potential for low-cost thermoelectric energy production using highly stable and inexpensive oxide materials.

Thermoelectric properties of non-stoichiometric MnTe compounds

Non-stoichiometric MnxTe1−x (x = 0.48–0.52) has been prepared by a melt-quench process followed by spark-plasma-sintering to investigate its thermoelectric properties. Polycrystalline MnxTe1−x with x > 0.51 has a nearly single MnTe phase. The measured Seebeck coefficient and electrical conductivity show a similar trend, in which a transition occurs near 473 K with increasing temperature. The thermal conductivity of MnxTe1−x compounds shows a tendency to decrease with increasing Mn content. Along with a low thermal conductivity and a high power factor, the samples with x > 0.51 have a high figure of merit, which reaches 0.41 at 773 K. The results indicate that production of a homogenous MnTe single phase is an effective way to improve the thermoelectric properties of p-type non-stoichiometric MnxTe1−x compounds.

Prediction of the band structures of Bi2Te3-related binary and Sb/Se-doped ternary thermoelectric materials

Density functional calculations are performed to study the band structures of Bi2Te3-related binary (Bi2Te3, Sb2Te3, Bi2Se3, and Sb2Se3) and Sb/Se-doped ternary compounds [(Bi1−xSbx)2Te3 and Bi2(Te1−ySey)3]. The band gap was found to be increased by Sb doping and to be monotonically increased by Se doping. In ternary compounds, the change in the conduction band structure is more significant as compared to the change in the valence band structure. The band degeneracy of the valence band maximum is maintained at 6 in binaries and ternaries. However, when going from Bi2Te3 to Sb2Te3 (Bi2Se3), the degeneracy of the conduction band minimum is reduced from 6 to 2(1). Based on the results for the band structures, we suggest suitable stoichiometries of ternary compounds for high thermoelectric performance.

Thermoelectric properties of SrTiO3 nano-particles dispersed indium selenide bulk composites

We investigated the thermoelectric properties of the InSe, InSe/In4Se3 composite, and SrTiO3 (STO) nano-particles dispersed InSe/In4Se3 bulk composites. The electrical conductivity of the InSe/In4Se3 composite with self-assembled phase separation is significantly increased compared with those of InSe and In4Se3–δ implying the enhancement of surface conductivity between grain boundaries. The thermal conductivity of InSe/In4Se3 composite is decreased compared to those of InSe. When the STO nano-particle dispersion was employed in the InSe/In4Se3 composite, a coherent interface was observed between nano-particle precipitates and the InSe bulk matrix with a reduction of the thermal conductivity.

Thermal Transport Driven by Extraneous Nanoparticles and Phase Segregation in Nanostructured Mg2(Si,Sn) and Estimation of Optimum Thermoelectric Performance

Solid solutions of magnesium silicide and magnesium stannide were recently reported to have high thermoelectric figure-of-merits (ZT) due to remarkably low thermal conductivity, which was conjectured to come from phonon scattering by segregated Mg2Si and Mg2Sn phases without detailed study. However, it is essential to identify the main cause for further improving ZT as well as estimating its upper bound. Here we synthesized Mg2(Si,Sn) with nanoparticles and segregated phases, and theoretically analyzed and estimated the thermal conductivity upon segregated fraction and extraneous nanoparticle addition by fitting experimentally obtained thermal conductivity, electrical conductivity, and thermopower. In opposition to the previous speculation that segregated phases intensify phonon scattering, we found that lattice thermal conductivity was increased by the phase segregation, which is difficult to avoid due to the miscibility gap. We selected extraneous TiO2 nanoparticles dissimilar to the host materials as additives to reduce lattice thermal conductivity. Our experimental results showed the maximum ZT was improved from ∼0.9 without the nanoparticles to ∼1.1 with 2 and 5 vol % TiO2 nanoparticles at 550 °C. According to our theoretical analysis, this ZT increase by the nanoparticle addition mainly comes from suppressed lattice thermal conductivity in addition to lower bipolar thermal conductivity at high temperatures. The upper bound of ZT was predicted to be ∼1.8 for the ideal case of no phase segregation and addition of 5 vol % TiO2 nanoparticles. We believe this study offers a new direction toward improved thermoelectric performance of Mg2(Si,Sn).

Enhancement of thermoelectric properties of Mg2Si compounds with Bi doping through carrier concentration tuning

AbstractThe Bi-doped Mg2Si powder was fabricated with solid state reaction method and consolidated with hot pressing method and then its thermoelectric properties were investigated. The n-type transport properties were measured in all samples and temperature dependence of the electrical properties shows a behavior of degenerate semiconductors for Bi-doped samples. The electrical resistivity and the Seebeck coefficient were greatly reduced with Bi, which was mainly due to the increment of the carrier concentration. The samples have maximum carrier concentration of 8.2 × 1018 cm−3. The largest ZT value of 0.61 was achieve at 873 K for Mg2.04SiBi0.02. The Bi-doping was found to be an effective n-type dopant to adjust carrier concentration.

Enhanced thermoelectric properties and development of nanotwins in Na-doped Bi0.5Sb1.5Te3 alloy

We found that Na is a good source to develop twin structures in the Bi-Te system, such as Ag as noted in a previous study. The twin boundaries had a considerable influence on reductions of the lattice thermal conductivity due to phonon scattering by the nano-ordered layers and on reductions of the electrical resistivity owing to the defects generated by the substitution of Na into the cation sites. Here, we report the enhanced thermoelectric properties of a Na-doped p-type Bi0.5Sb1.5Te3 alloy. Measurements show that the electrical resistivity and the Seebeck coefficient decrease with Na doping due to an increase in the free carrier (hole) concentration and that the lattice thermal conductivity decreases with Na doping. The achieved maximum ZT value was 1.20 at 423 K, which is approximately 20% higher than that of Bi0.5Sb1.5Te3 under the same fabrication conditions. These results were achievable by controlling the morphology of the twin structure and the carrier concentration by means of Na doping.

Defects responsible for abnormal n-type conductivity in Ag-excess doped PbTe thermoelectrics

Density functional calculations have been performed to investigate the role of Ag defects in PbTe thermoelectric materials. Ag-defects can be either donor, acceptor, or isovalent neutral defect. When Ag is heavily doped in PbTe, the neutral (Ag-Ag) dimer defect at Pb-site is formed and the environment changes to the Pb-rich/Te-poor condition. Under Pb-rich condition, the ionized Ag-interstitial defect (Ag I +) becomes the major donor. The formation energy of Ag I + is smaller than other native and Ag-related defects. Also it is found that Ag I + is an effective dopant. There is no additional impurity state near the band gap and the conduction band minimum. The charge state of Ag I + defect is maintained even when the Fermi level is located above the conduction band minimum. The diffusion constant of Ag I + is calculated based on the temperature dependent Fermi level, formation energy, and migration energy. When T > 550 K, the diffusion length of Ag within a few minutes is comparable to the grain size of the polycrystalline PbTe, implying that Ag is dissolved into PbTe and this donor defect is distributed over the whole lattice in Ag-excess doped polycrystalline PbTe. The predicted solubility of Ag I + well explains the increased electron carrier concentration and electrical conductivity reported in Ag-excess doped polycrystalline PbTe at T = 450–750 K [Pei et al., Adv. Energy Mater. 1, 291 (2011)]. In addition, we suggest that this abnormal doping behavior is also found for Au-doped PbTe.

Hybrid-density functional theory study on the band structures of tetradymite-Bi2Te3, Sb2Te3, Bi2Se3, and Sb2Se3 thermoelectric materials

The low-energy band structure near the band gap determines the electrical performance of thermoelectric materials. Here, by using the hybrid-density functional theory (hybrid-DFT) calculations, we calculate the low-energy band structure of Bi2Te3, Sb2Te3, Bi2Se3 and Sb2Se3 in the tetradymite phase. We find that the band structure characteristics are very sensitive the selection of the exchange energy functional. The predictability of the band gaps and the band degeneracies is not enhanced in hybrid-DFT calculations, as compared to DFT calculations. The poor prediction of low-energy band structures originates from the poor prediction of interlayer distances and the high structure sensitivity on the band gap. We conclude that the hybrid-DFT calculations are not superior to DFT calculations when predicting band structures of tetradymite Bi2Te3, Sb2Te3, Bi2Se3 and Sb2Se3 thermoelectric materials.