Cross-plane electronic and thermal transport properties of p-type La0.67Sr0.33MnO3/LaMnO3 perovskite oxide metal/semiconductor superlattices

Lanthanum strontium manganate (La0.67Sr0.33MnO3, i.e., LSMO)/lanthanum manganate (LaMnO3, i.e., LMO) perovskite oxide metal/semiconductor superlattices were investigated as a potential p-type thermoelectric material. Growth was performed using pulsed laser deposition to achieve epitaxial LSMO (metal)/LMO (p-type semiconductor) superlattices on (100)-strontium titanate (STO) substrates. The magnitude of the in-plane Seebeck coefficient of LSMO thin films (/K) is consistent with metallic behavior, while LMO thin films were p-type with a room temperature Seebeck coefficient of 140 mu V/K. Thermal conductivity measurements via the photo-acoustic (PA) technique showed that LSMO/LMO superlattices exhibit a room temperature cross-plane thermal conductivity (0.89 W/m.K) that is significantly lower than the thermal conductivity of individual thin films of either LSMO (1.60 W/m.K) or LMO (1.29 W/m.K). The lower thermal conductivity of LSMO/LMO superlattices may help overcome one of the major limitations of oxides as thermoelectrics. In addition to a low cross-plane thermal conductivity, a high ZT requires a high power factor (S-2 sigma). Cross-plane electrical transport measurements were carried out on cylindrical pillars etched in LSMO/LMO superlattices via inductively coupled plasma reactive ion etching. Cross-plane electrical resistivity data for LSMO/LMO superlattices showed a magnetic phase transition temperature (T-P) or metal-semiconductor transition at similar to 330 K, which is similar to 80K higher than the T-P observed for in-plane resistivity of LSMO, LMO, or LSMO/LMO thin films. The room temperature cross-plane resistivity (rho(c)) was found to be greater than the in-plane resistivity by about three orders of magnitude. The magnitude and temperature dependence of the cross-plane conductivity of LSMO/LMO superlattices suggests the presence of a barrier with the effective barrier height of similar to 300 meV. Although the magnitude of the cross-plane power factor is too low for thermoelectric applications by a factor of approximately 10(-4)-in part because the growth conditions chosen for this study yielded relatively high resistivity films-the temperature dependence of the resistivity and the potential for tuning the power factor by engineering strain, oxygen stoichiometry, and electronic band structure suggest that these epitaxial metal/semiconductor superlattices are deserving of further investigation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4754514

High temperature experimental characterization of microscale thermoelectric effects

Thermoelectric devices have been employed for many years as a reliable energy conversion technology for applications ranging from the cooling of sensors or charge coupled devices to the direct conversion of heat into electricity for remote power generation. However, its relatively low conversion efficiency has limited the implementation of thermoelectric materials for large scale cooling and waste heat recovery applications. Recent advances in semiconductor growth technology have enabled the precise and selective engineering of material properties to improve the thermoelectric figure of merit and thus the efficiency of thermoelectric devices. Accurate characterization at the intended operational temperature of novel thermoelectric materials is a crucial component of the optimization process in order to fundamentally understand material behavior and evaluate performance. The objective of this work is to provide the tools necessary to characterize high efficiency bulk and thin-film materials for thermoelectric energy conversion. The techniques developed here are not bound to specific material or devices, but can be generalized to any material system. Thermoreflectance imaging microscopy has proven to be invaluable for device thermometry owing to its high spatial and temporal resolutions. It has been utilized in this work to create two-dimensional temperature profiles of thermoelectric devices during operation used for performance analysis of novel materials, identification of defects, and visualization of high speed transients in a high-temperature imaging thermostat. We report the development of a high temperature imaging thermostat capable of high speed transient thermoelectric characterization. In addition, we present a noninvasive method for thermoreflectance coefficient calibration ideally suited for vacuum and thus high temperature employment. This is the first analysis of the thermoreflectance coefficient of commonly used metals at high-temperatures. High temperature vacuum thermostats are designed and fabricated with optical imaging capability and interchangeable measurement stages for various electrical and thermoelectric characterizations. We demonstrate the simultaneous measurement of in-plane electrical conductivity and Seebeck coefficient of thin-film or bulk thermoelectric materials. Furthermore, we utilize high-speed circuitry to implement the transient Harman technique and directly determine the cross-plane figure of merit of thin film thermoelectric materials at high temperatures. Transient measurements on thin film devices are subject to complications from the growth substrate, non-ideal contacts and other detrimental thermal and electrical effects. A strategy is presented for optimizing device geometry to mitigate the impact of these parasitics. This design enabled us to determine the cross-plane thermoelectric material properties in a single high temperature measurement of a 25μm InGaAs thin film with embedded ErAs (0.2%) nanoparticles using the bipolar transient Harman technique in conjunction with thermoreflectance thermal imaging. This approach eliminates discrepancies and potential device degradation from the multiple measurements necessary to obtain individual material parameters. Finite element method simulations are used to analyze non-uniform current and temperature distributions over the device area and determine the three dimensional current path for accurate extraction of material properties from the thermal images. Results match with independent measurements of thermoelectric material properties for the same material composition, validating this approach. We apply high magnification thermoreflectance imaging to create temperature maps of vanadium dioxide nanobeams and examine electro-thermal energy conversion along the nanobeam length. The metal to insulator transition of strongly correlated materials is subject to strong lattice coupling which brings about the unique one-dimensional alignment of metal-insulator domains along nanobeams. Many studies have investigated the effects of stress on the metal to insulator transition and hence the phase boundary, but few have directly examined the temperature profile across the metal-insulating interface. Here, thermoreflectance microscopy reveals the underlying behavior of single-crystalline VO2 nanobeams in the phase coexisting regime. We directly observe highly localized alternating Peltier heating and cooling as well as Joule heating concentrated at the domain interfaces, indicating the significance of the domain walls and band offsets. Moreover, we are able to elucidate strain accumulation along the nanobeam and distinguish between two insulating phases of VO 2 through detection of the opposite polarity of their respective thermoreflectance coefficients

Cross-plane thermoelectric transport in p-type La0.67Sr0.33MnO3/LaMnO3 oxide metal/semiconductor superlattices

The cross-plane thermoelectric transport properties of La0.67Sr0.33MnO3 (LSMO)/LaMnO3 (LMO) oxide metal/semiconductor superlattices were investigated. The LSMO and LMO thin-film depositions were performed using pulsed laser deposition to achieve low resistivity constituent materials for LSMO/LMO superlattice heterostructures on (100)-strontium titanate substrates. X-ray diffraction and high-resolution reciprocal space mapping indicate that the superlattices are epitaxial and pseudomorphic. Cross-plane devices were fabricated by etching cylindrical pillar structures in superlattices using inductively, this coupled-plasma reactive-ion etching. The crossplane electrical conductivity data for LSMO/LMO superlattices reveal a lowering of the effective barrier height to 223 meV as well as an increase in cross-plane conductivity by an order of magnitude compared to high resistivity superlattices. These results suggest that controlling the oxygen deficiency in the constituent materials enables modification of the effective barrier height and increases the cross-plane conductivity in oxide superlattices. The cross-plane LSMO/LMO superlattices showed a giant Seebeck coefficient of 2560 mu V/K at 300K that increases to 16 640 mu V/K at 360 K. The giant increase in the Seebeck coefficient with temperature may include a collective contribution from the interplay of charge, spin current, and phonon drag. The low resistance oxide superlattices exhibited a room temperature cross-plane thermal conductivity of 0.92W/mK, this indicating that the suppression of thermal conductivities due to the interfaces is preserved in both low and high resistivity superlattices. The high Seebeck coefficient, the order of magnitude improvement in cross-plane conductivity, and the low thermal conductivity in LSMO/LMO superlattices resulted in a two order of magnitude increase in cross-plane power factor and thermoelectric figure of merit (ZT), compared to the properties of superlattices with higher resistivity that were reported previously. The temperature dependence of the cross-plane power factor in low resistance superlattices suggests a direction for further investigations of the potential LSMO/LMO oxide superlattices for thermoelectric devices. (C) 2013 AIP Publishing LLC

Thermoelectric properties of epitaxial ScN films deposited by reactive magnetron sputtering onto MgO(001) substrates

Epitaxial ScN(001) thin films were grown on MgO(001) substrates by dc reactive magnetron sputtering. The deposition was performed in an Ar/N-2 atmosphere at 2 x 10(-3) Torr at a substrate temperature of 850 degrees C in a high vacuum chamber with a base pressure of 10(-8) Torr. In spite of oxygen contamination of 1.6 +/- 1 at. %, the electrical resistivity, electron mobility, and carrier concentration obtained from a typical film grown under these conditions by room temperature Hall measurements are 0.22 m Omega cm, 106 cm(2) V-1 s(-1), and 2.5 x 10(20) cm(-3), respectively. These films exhibit remarkable thermoelectric power factors of 3.3-3.5 x 10(-3) W/mK(2) in the temperature range of 600 K to 840 K. The cross-plane thermal conductivity is 8.3 W/mK at 800 K yielding an estimated ZT of 0.3. Theoretical modeling of the thermoelectric properties of ScN calculated using a mean-free-path of 23 nm at 300 K is in very good agreement with the experiment. These results also demonstrate that further optimization of the power factor of ScN is possible. First-principles density functional theory combined with the site occupancy disorder technique was used to investigate the effect of oxygen contamination on the electronic structure and thermoelectric properties of ScN. The computational results suggest that oxygen atoms in ScN mix uniformly on the N site forming a homogeneous solid solution alloy. Behaving as an n-type donor, oxygen causes a shift of the Fermi level in ScN into the conduction band without altering the band structure and the density of states. (C) 2013 AIP Publishing LLC [http://dx.doi.org/10.1063/1.4801886

Direct Observation of Nanoscale Peltier and Joule Effects at Metal-Insulator Domain Walls in Vanadium Dioxide Nanobeams

The metal to insulator transition (MIT) of strongly correlated materials is subject to strong lattice coupling, which brings about the unique one-dimensional alignment of metal insulator (M-I) domains along nanowires or nanobeams. Many studies have investigated the effects of stress on the MIT and hence the phase boundary, but few have directly examined the temperature profile across the metal insulating interface. Here, we use thermoreflectance microscopy to create two-dimensional temperature maps of single-crystalline VO2 nanobeams under external bias in the phase coexisting regime. We directly observe highly localized alternating Peltier heating and cooling as well as Joule heating concentrated at the M I domain boundaries, indicating the significance of the domain walls and band offsets. Utilizing the thermoreflectance technique, we are able to elucidate strain accumulation along the nanobeam and distinguish between two insulating phases of VO2 through detection of the opposite polarity of their respective thermoreflectance coefficients. Microelasticity theory was employed to predict favorable domain wall configurations, confirming the monoclinic phase identification