skip to main content


Title: Thermal stability of self-assembled ordered three-phase Au–BaTiO 3 –ZnO nanocomposite thin films via in situ heating in TEM
Thermal stability of oxide–metal nanocomposites is important for designing practical devices for high temperature applications. Here, we study the thermal stability of the self-assembled ordered three-phase Au–BaTiO 3 –ZnO nanocomposite by both ex situ annealing under air and vacuum conditions, and by in situ heating in TEM in a vacuum. The study reveals that the variation of the annealing conditions greatly affects the resulting microstructure and the associated dominant diffusion mechanism. Specifically, Au nanoparticles show coarsening upon air annealing, while Au and Zn either form a solid solution, with Zn atomic percentage less than 10%, or undergo a reverse Vapor–Liquid–Solid (VLS) mechanism upon vacuum annealing. The distinct microstructures obtained also show different permittivity response in the visible and near-infrared region, while retaining their hyperbolic dispersion characteristics enabled by their highly anisotropic structures. Such in situ heating study in TEM provides critical information about microstructure evolution, growth mechanisms at the nanoscale, and thermal stability of the multi-phase nanocomposites for future electronic device applications.  more » « less
Award ID(s):
2016453 1565822
NSF-PAR ID:
10226867
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Nanoscale
Volume:
12
Issue:
46
ISSN:
2040-3364
Page Range / eLocation ID:
23673 to 23681
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Flash pyrolysis, which combines conventional pyrolysis with flash sintering, was first conducted to produce polymer derived SiC‐TiC nanocomposites. Pre‐pyrolysis at 800℃ allows the conversion from titanium isopropoxide (TTIP) modified polysiloxane to an amorphous SiTiOC ceramic. The subsequent application of an electric field gives rise to the formation of turbostratic carbon and creates Joule heating to obtain a sample internal temperature of ~1400℃. The precipitation of β‐SiC, TiC, as well as titanium oxides is realized upon carbothermal reduction of extensively phase separated SiO2and TiO2with carbon. Increasing TTIP content embodies the nanocomposites with prominent electrical percolation behaviors. The electrical transport of the synthesized ceramics follows an amorphous semiconductor mechanism. High thermal stability in air is guaranteed, thanks to the in‐situ formed TiC nanocrystals and preferentially reduced amorphous carbon. Flash pyrolyzed nanocomposite with a Ti:Si molar ratio of 0.20 exhibits the highest electrical conductivity (0.696 S/cm) and minimum mass change (~2%) at 1000℃, serving as a competitive candidate for electro‐discharge machining (EDM) applications or self‐standing conducting devices that must withstand high temperature conditions.

     
    more » « less
  2. Abstract

    Heat transport across vertical interfaces of heterogeneous 2D materials is usually governed by the weak Van der Waals interactions of the surface‐terminating atoms. Such interactions play a significant role in thermal transport across transition metal carbide and nitride (MXene) atomic layers due to their hydrophilic nature and variations in surface terminations. Here, the metallicity of atomically thin Ti3C2TzMXene, which is also verified by scanning tunneling spectroscopy for the first time, is exploited to develop a self‐heating/self‐sensing platform to carry out direct‐current annealing experiments in high (<10−8bar) vacuum, while simultaneously evaluating the interfacial heat transport across a Ti3C2Tz/SiO2interface. At room temperature, the thermal boundary conductance (TBC) of this interface is found, on average, to increase from 10 to 27 MW m−2K−1upon current annealing up to the breakdown limit. In situ heating X‐ray diffraction and X‐ray photo‐electron spectroscopy reveal that the TBC values are mainly affected by interlayer and interface spacing due to the removal of absorbents, while the effect of surface termination is negligible. This study provides key insights into understanding energy transport in MXene nanostructures and other 2D material systems.

     
    more » « less
  3. Ni-SiOC nanocomposites maintain crystal-amorphous dual-phase nanostructures after high-temperature annealing at different temperatures (600 °C, 800 °C and 1000 °C), while the feature sizes of crystal Ni and amorphous SiOC increase with the annealing temperature. Corresponding to the dual-phase nanostructures, Ni-SiOC nanocomposites exhibit a high strength and good plastic flow stability. In this study, we conducted a He implantation in Ni-SiOC nanocomposites at 300 °C by in-situ transmission electron microscope (TEM) irradiation test. In-situ TEM irradiation revealed that both crystal Ni and amorphous SiOC maintain stability under He irradiation. The 600 °C annealed sample presents a better He irradiation resistance, as manifested by a smaller He-bubble size and lower density. Both the grain boundary and crystal-amorphous phase boundary act as a sink to absorb He and irradiation-induced defects in the Ni matrix. More importantly, amorphous SiOC ceramic is immune to He irradiation damage, contributing to the He irradiation resistance of Ni alloy.

     
    more » « less
  4. In the present study, thermal stability of α-Ga2O3 under vacuum and ambient pressure conditions was investigated in situ by x-ray diffraction and transmission electron microscopy (TEM). It was observed that the thermal stability of α-Ga2O3 increased by 200 °C when pressure was lowered from an atmospheric to a vacuum level. This finding can be explained by oxygen diffusion under different oxygen partial pressures. In addition, in situ TEM imaging revealed that, once past the decomposition temperature, the onset of phase change propagates from the top crystal surface and accumulates strain, eventually resulting in a fractural film. The mechanism of α-Ga2O3 to β-Ga2O3 transition is evaluated through experiments and is discussed in this manuscript.

     
    more » « less
  5. 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 in 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. 
    more » « less