skip to main content

This content will become publicly available on December 21, 2022

Title: Observation of suppressed diffuson and propagon thermal conductivity of hydrogenated amorphous silicon films
Hydrogenated amorphous silicon (a-Si:H) has drawn keen interest as a thin-film semiconductor and superb passivation layer in high-efficiency silicon solar cells due to its low cost, low processing temperature, high compatibility with substrates, and scalable manufacturing. Although the impact of hydrogenation on the structural, optical, and electronic properties of a-Si:H has been extensively studied, the underlying physics of its impact on the thermal properties is still unclear. Here, we synthesize a-Si:H films with well-controlled hydrogen concentrations using plasma-enhanced chemical vapor deposition and systematically study the thermal conductivity of these a-Si:H films using time-domain thermoreflectance. We find that the reduction of thermal conductivity of a-Si:H films is attributed to the suppression of diffuson and propagon contributions as the hydrogen concentration increases. At the maximum hydrogen concentration of 25.4 atomic percentage, the contributions from diffusons and propagons to the thermal conductivity are decreased by 40% (from 1.10 to 0.67 W m −1 K −1 ) and 64% (from 0.61 to 0.22 W m −1 K −1 ), respectively. Such a significant reduction in the thermal conductivity of a-Si:H originates from the hydrogen induced material softening, the decrease in density, and phonon-defect scattering. The results of this work provide fundamental insights into the more » thermal transport properties of a-Si:H thin films, which is beneficial for the design and optimization of amorphous silicon-based technologies including photovoltaics, large-area electronics, and thermoelectric devices. « less
Authors:
; ; ; ;
Award ID(s):
2011401
Publication Date:
NSF-PAR ID:
10323948
Journal Name:
Nanoscale Advances
Volume:
4
Issue:
1
Page Range or eLocation-ID:
87 to 94
ISSN:
2516-0230
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Amorphous chalcogenide alloys are key materials for data storage and energy scavenging applications due to their large non-linearities in optical and electrical properties as well as low vibrational thermal conductivities. Here, we report on a mechanism to suppress the thermal transport in a representative amorphous chalcogenide system, silicon telluride (SiTe), by nearly an order of magnitude via systematically tailoring the cross-linking network among the atoms. As such, we experimentally demonstrate that in fully dense amorphous SiTe the thermal conductivity can be reduced to as low as 0.10 ± 0.01 W m −1 K −1 for high tellurium content with a density nearly twice that of amorphous silicon. Using ab-initio simulations integrated with lattice dynamics, we attribute the ultralow thermal conductivity of SiTe to the suppressed contribution of extended modes of vibration, namely propagons and diffusons. This leads to a large shift in the mobility edge - a factor of five - towards lower frequency and localization of nearly 42% of the modes. This localization is the result of reductions in coordination number and a transition from over-constrained to under-constrained atomic network.
  2. Controlling nanoporosity to favorably alter multiple properties in layered crystalline inorganic thin films is a challenge. Here, we demonstrate that the thermoelectric and mechanical properties of Ca 3 Co 4 O 9 films can be engineered through nanoporosity control by annealing multiple Ca(OH) 2 /Co 3 O 4 reactant bilayers with characteristic bilayer thicknesses (b t ). Our results show that doubling b t , e.g. , from 12 to 26 nm, more than triples the average pore size from ∼120 nm to ∼400 nm and increases the pore fraction from 3% to 17.1%. The higher porosity film exhibits not only a 50% higher electrical conductivity of σ ∼ 90 S cm −1 and a high Seebeck coefficient of α ∼ 135 μV K −1 , but also a thermal conductivity as low as κ ∼ 0.87 W m −1 K −1 . The nanoporous Ca 3 Co 4 O 9 films exhibit greater mechanical compliance and resilience to bending than the bulk. These results indicate that annealing reactant multilayers with controlled thicknesses is an attractive way to engineer nanoporosity and realize mechanically flexible oxide-based thermoelectric materials.
  3. This work presents an energy efficient technique for fabricating flexible thermoelectric generators while using printable ink. We have fabricated thermoelectric composite thick films using two different mesh sizes of n-type bismuth particles, various binder to thermoelectric material weight ratios, and two different pressures, 200 MPa and 300 MPa, in order to optimize the thermoelectric properties of the composite films. The use of chitosan dissolved in dimethylsulfoxide with less than 0.2 wt. % of chitosan, the first time chitosan has been used in this process, was sufficient for fabricating TE inks and composite films. Low temperature curing processes, along with uniaxial pressure, were used to evaporate the solvent from the drop-casted inks. This combination reduced the temperature needed compared to traditional curing processes while simultaneously increasing the packing density of the film by removing the pores and voids in the chitosan-bismuth composite film. Microstructural analysis of the composite films reveals low amounts of voids and pores when pressed at sufficiently high pressures. The highest performing composite film was obtained with the weight ratio of 1:2000 binder to bismuth, 100-mesh particle size, and 300 MPa of pressure. The best performing bismuth chitosan composite film that was pressed at 300 MPa had amore »power factor of 4009 ± 391 μW/m K2 with high electrical conductivity of 7337 ± 522 S/cm. The measured thermal conductivity of this same sample was 4.4 ± 0.8 W/m K and the corresponding figure of merit was 0.27 at room temperature.« less
  4. Recent work has demonstrated a low-temperature route to fabricating mixed ionic/electronic conducting (MIEC) thin films with enhanced oxygen exchange kinetics by crystallizing amorphous-grown thin films under mild temperatures, eluding conditions for deleterious A-site cation surface segregation. Yet, the complex, multiscale chemical and structural changes during MIEC crystallization and their implications for the electrical properties remain relatively unexplored. In this work, micro-structural and atomic-scale structural and chemical changes in crystallizing SrTi 0.65 Fe 0.35 O 3− δ thin films on insulating (0001)-oriented Al 2 O 3 substrates are observed and correlated to changes in the in-plane electrical conductivity, measured in situ by ac impedance spectroscopy. Synchrotron X-ray absorption spectroscopy at the Fe and Ti K-edges gives direct evidence of oxidation occurring with the onset of crystallization and insight into the atomic-scale structural changes driven by the chemical changes. The observed oxidation, increase in B-site polyhedra symmetry, and alignment of neighboring B-site cation coordination units demonstrate increases in both hole concentration and mobility, thus underpinning the measured increase of in-plane conductivity by over two orders of magnitude during crystallization. High resolution transmission electron microscopy and spectroscopy of films at various degrees of crystallinity reveal compositional uniformity with extensive nano-porosity in the crystallizedmore »films, consistent with solid phase contraction expected from both oxidation and crystallization. We suggest that this chemo-mechanically driven dynamic nano-structuring is an additional contributor to the observed electrical behavior. By the point that the films become ∼60% crystalline (according to X-ray diffraction), the conductivity reaches the value of dense, fully crystalline films. Given the resulting high electronic conductivity, this low-temperature processing route leading to semi-crystalline hierarchical films exhibits promise for developing high performance MIECs for low-to-intermediate temperature applications.« less
  5. Light elements in Earth’s core play a key role in driving convection and influencing geodynamics, both of which are crucial to the geodynamo. However, the thermal transport properties of iron alloys at high-pressure and -temperature conditions remain uncertain. Here we investigate the transport properties of solid hexagonal close-packed and liquid Fe-Si alloys with 4.3 and 9.0 wt % Si at high pressure and temperature using laser-heated diamond anvil cell experiments and first-principles molecular dynamics and dynamical mean field theory calculations. In contrast to the case of Fe, Si impurity scattering gradually dominates the total scattering in Fe-Si alloys with increasing Si concentration, leading to temperature independence of the resistivity and less electron–electron contribution to the conductivity in Fe-9Si. Our results show a thermal conductivity of ∼100 to 110 W⋅m −1 ⋅K −1 for liquid Fe-9Si near the topmost outer core. If Earth’s core consists of a large amount of silicon (e.g., > 4.3 wt %) with such a high thermal conductivity, a subadiabatic heat flow across the core–mantle boundary is likely, leaving a 400- to 500-km-deep thermally stratified layer below the core–mantle boundary, and challenges proposed thermal convection in Fe-Si liquid outer core.