skip to main content

This content will become publicly available on February 1, 2023

Title: Multi-scale chemo-mechanical evolution during crystallization of mixed conducting SrTi 0.65 Fe 0.35 O 3−δ films and correlation to electrical conductivity
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 crystallized more » 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
; ; ; ;
Award ID(s):
Publication Date:
Journal Name:
Journal of Materials Chemistry A
Page Range or eLocation-ID:
2421 to 2433
Sponsoring Org:
National Science Foundation
More Like this
  1. To understand the mechanism underlying the fast, reversible, phase transformation, information about the atomic structure and defects structures in phase change materials class is key. PCMs are investigated for many applications. These devices are chalcogenide based and use self heating to quickly switch between amorphous and crystalline phases, generating orders of magnitude differences in the electrical resistivity. The main challenges with PCMs have been the large power required to heat above crystallization or melting (for melt-quench amorphization) temperatures and limited reliability due to factors such as resistance drifts of the metastable phases, void formation and elemental segregation upon cycling. Characterization of devices and their unique switching behavior result in distinct material properties affected by the atomic arrangement in the respective phase. TEM is used to study the atomic structure of the metastable crystalline phase. The aim is to correlate the microstructure with results from electrical characterization, building on R vs T measurements on various thicknesses GST thin films. To monitor phase changes in real-time as a function of temperature, thin films are deposited directly onto Protochips carriers. The Protochips heating holders provides controlled temperature changes while imaging in the TEM. These studies can provide insights into how changes occur inmore »the various phase transformations even though the rate of temperature change is much slower than the PCM device operation. Other critical processes such as void formation, grain evolution and the cause of resistance drift can thereby be related to changes in structure and chemistry. Materials characterization is performed using Tecnai F30 and Titan ETEM microscopes, operating at 300kV. Both the microscopes can accept the same Protochips heating holders. The K2 direct electron detector camera equipped with the ETEM allows high-speed video recording (1600 f/s) of structural changes occurring in these materials upon heating and cooling. In this presentation, we will describe the effect of heating thin films of different thickness and composition, the changes in crystallinity and grain size, and how these changes correlate with changes in the electrical properties of the films. We will emphasize that it is always important to use low-dose and/or beam blanking techniques to distinguish changes induced by the beam from those due to the heating or introduction of an electric current.« less
  2. In this work, the structural and electrical properties of metalorganic chemical vapor deposited Si-doped β-(Al x Ga 1−x ) 2 O 3 thin films grown on (010) β-Ga 2 O 3 substrates are investigated as a function of Al composition. The room temperature Hall mobility of 101 cm 2 /V s and low temperature peak mobility (T = 65 K) of 1157 cm 2 /V s at carrier concentrations of 6.56 × 10 17 and 2.30 × 10 17  cm −3 are measured from 6% Al composition samples, respectively. The quantitative secondary ion mass spectroscopy (SIMS) characterization reveals a strong dependence of Si and other unintentional impurities, such as C, H, and Cl concentrations in β-(Al x Ga 1−x ) 2 O 3 thin films, with different Al compositions. Higher Al compositions in β-(Al x Ga 1−x ) 2 O 3 result in lower net carrier concentrations due to the reduction of Si incorporation efficiency and the increase of C and H impurity levels that act as compensating acceptors in β-(Al x Ga 1−x ) 2 O 3 films. Lowering the growth chamber pressure reduces Si concentrations in β-(Al x Ga 1−x ) 2 O 3 films due to the increase of Al compositions as evidenced by comprehensive SIMS and Hallmore »characterizations. Due to the increase of lattice mismatch between the epifilm and substrate, higher Al compositions lead to cracking in β-(Al x Ga 1−x ) 2 O 3 films grown on β-Ga 2 O 3 substrates. The (100) cleavage plane is identified as a major cracking plane limiting the growth of high-quality Si-doped (010) β-(Al x Ga 1−x ) 2 O 3 films beyond the critical thicknesses, which leads to highly anisotropic and inhomogeneous behaviors in terms of conductivity.« less
  3. A magnetron co-sputtering system was used for producing nickel-doped Ge2Sb2Te5 (GST-Ni) thin films. The nickel content in the thin film was adjusted by the ratio of the plasma discharge power applied to the GST and nickel targets, as well as a physical shuttering technique to further control the nickel deposition rate. The doping concentration of the film was con firmed using Energy Dispersion Spectroscopy (EDS) technique. Results from a four-point probe measurement indicate that the nickel doping can reduce the resistivity of GST in the amorphous state by nearly three orders of magnitude. The dopant's influence on crystallization behavior was studied by analyzing X-Ray Diffraction (XRD) patterns of the pure GST and GST-Ni at different annealing temperatures. To examine the structural changes due to the nickel dopant, the thin films were investigated with the aid of Raman scattering. Additionally, we extracted the optical constants for both the amorphous and crystalline states of undoped-GST and GST-Ni films by ellipsometry. The results indicate that at low doping concentrations nickel does not appreciably affect the optical constants, but dramatically improves the electrical conductivity. Therefore, nickel-doping of GST a viable method for designing optical devices for lower operating voltages at higher switching speeds.
  4. Abstract

    Large area highly crystalline MoS2and WS2thin films were successfully grown on different substrates using radio-frequency magnetron sputtering technique. Structural, morphological and thermoelectric transport properties of MoS2,and WS2thin films have been investigated systematically to fabricate high-efficient thermal energy harvesting devices. X-ray diffraction data revealed that crystallites of MoS2and WS2films are highly oriented in 002 plane with uniform grain size distribution confirmed through atomic force microscopy study. Surface roughness increases with substrate temperature and it plays a big role in electron and phonon scattering. Interestingly, MoS2films also display low thermal conductivity at room temperature and strongly favors achievement of higher thermoelectric figure of merit value of up to 1.98. Raman spectroscopy data shows two distinct MoS2vibrational modes at 380 cm−1for E12gand 410 cm−1for A1g. Thermoelectric transport studies further demonstrated that MoS2films show p-type thermoelectric characteristics, while WS2is an n-type material. We demonstrated high efficient pn-junction thermoelectric generator device for waste heat recovery and cooling applications.

  5. We report the synthesis and characterization of as-grown SrFexMn1-xO2.5 epitaxial films, which were also subjected to post-growth oxidation and topotactic fluorination to obtain SrFexMn1-xO3 and SrFexMn1-xO(2.5-d)Fg films. We show how both the B-site cation and anion composition influence the structural, electronic, and optical properties of this family of perovskite materials. The Fe substitution of Mn in SrMnO2.5 gradually expands the c-axis parameter, as indicated by X-ray diffraction. With increasing x, the F content incorporated under identical fluorination conditions increases, reaching its maximum in SrFeO(2.5-d)Fg. In the compounds with mixed B-site occupation, the Fe 2p photoemission peaks are shifted upon fluorination while the Mn 2p peaks are not, suggesting inductive effects lead to asymmetric responses in how F alters the Mn and Fe bonds. Electronic transport measurements reveal all compounds are insulators, with the exception of SrFeO3, and demonstrate that fluorination increases resistivity for all values of x. Optical absorption spectra in the SrFexMn1-xO2.5 and SrFexMn1-xO3 films evolve systematically as a function of x, consistent with a physical scenario in which optical changes with Fe substitution arise from a linear combination of Mn and Fe 3d bands within the electronic structure. In contrast, the F incorporation induces non-linear changes to themore »optical response, suggesting a more complex impact on the electronic structure in materials with concurrent B-site and anion site substitution.« less