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.
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The Effects of Size and Shape Dispersity on the Phase Behavior of Nanomesogen Lyotropic Liquid Crystals
Self-assembly of anisotropic nanomaterials into fluids is a key step in producing bulk, solid materials with controlled architecture and properties. In particular, the ordering of anisotropic nanomaterials in lyotropic liquid crystalline phases facilitates the production of films, fibers, and devices with anisotropic mechanical, thermal, electrical, and photonic properties. While often considered a new area of research, experimental and theoretical studies of nanoscale mesogens date back to the 1920s. Through modern computational, synthesis, and characterization tools, there are new opportunities to design liquid crystalline phases to achieve complex architectures and enable new applications in opto-electronics, multifunctional textiles, and conductive films. This review article provides a brief review of the liquid crystal phase behavior of one dimensional nanocylinders and two dimensional nanoplatelets, a discussion of investigations on the effects of size and shape dispersity on phase behavior, and outlook for exploiting size and shape dispersity in designing materials with controlled architectures.
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- Award ID(s):
- 2005413
- NSF-PAR ID:
- 10252930
- Date Published:
- Journal Name:
- Crystals
- Volume:
- 10
- Issue:
- 8
- ISSN:
- 2073-4352
- Page Range / eLocation ID:
- 715
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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The size and shape of polymer materials is becoming an increasingly important property in accessing new functions and applications of nano‐/microparticles in many scientific fields. New synthetic methods have allowed unprecedented capability for the facile fabrication of anisotropic and shape‐defined nanomaterials. Bottom‐up approaches including: emulsion polymerization techniques, amphiphile self‐assembly, and polymerization‐induced self‐assembly, can lead to polymer particles with precise dimensions in the nanoscale. Top‐down methods such as lithographic templating, and 3D printing, have increased the access to unique particle shapes. In this review, these recent developments are appraised and contrasted, with future research directions providing that focus on biomedical applications. Finally, the opportunity available for synergistic combinations of top‐down and bottom‐up fabrication approaches in realizing previously unattainable architectures and material properties is highlighted.
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Abstract Microreactor-Assisted Nanomaterial Deposition (MAND) process offers unique capabilities in achieving large size and shape control levels while providing a more rapid path for scaling via process intensification for nanomaterial production. This review highlights the application of continuous flow microreactors to synthesize, assemble, transform, and deposit nanostructured materials for Solar Photovoltaics, the capabilities of MAND in the field, and the potential outlook of MAND Microreactor-Assisted Nanomaterial Deposition (MAND) is a promising technology that synthesizes reactive fluxes and nanomaterials to deposit nanostructured materials at the point of use. MAND offers precise control over reaction, organization, and transformation processes to manufacture nanostructured materials with distinct morphologies, structures, and properties. In synthesis, microreactor technology offers large surface-area-to-volume ratios within microchannel structures to accelerate heat and mass transport. This accelerated transport allows for rapid changes in reaction temperatures and concentrations, leading to more uniform heating and mixing in the deposition process. The possibility of synthesizing nanomaterials in the required volumes at the point of application eliminates the need to store and transport potentially hazardous materials. Further, MAND provides new opportunities for tailoring novel nanostructures and nano-shaped features, opening the opportunity to assemble unique nanostructures and nanostructured thin films. MAND processes control the heat transfer, mass transfer, and reaction kinetics using well-defined microstructures of the active unit reactor cell that can be replicated at larger scales to produce higher chemical production volumes. This critical feature opens a promising avenue in developing scalable nanomanufacturing. This paper reviews advances in microreactor-assisted nanomaterial deposition of nanostructured materials for solar photovoltaics. The discussions review the use of microreactors to tailor the reacting flux, transporting to substrate surfaces via controlling process parameters such as flow rates, pH of the precursor solutions, and seed layers on the formation and/or transformation of intermediary reactive molecules, nanoclusters, nanoparticles, and structured assemblies. In the end, the review discusses the use of an industrial scale MAND to apply anti-reflective and anti-soiling coatings on the solar modules in the field and details future outlooks of MAND reactors.
Graphical abstract -
Crystallization is incommensurate with nanoscale curved space due to the lack of three dimensional translational symmetry of the latter. Herein, we report the formation of single-crystal-like, nanosized polyethylene (PE) capsules using a miniemulsion solution crystallization method. The miniemulsion was formed at elevated temperatures using PE organic solution as the oil phase and sodium dodecyl sulfate as the surfactant. Subsequently, cooling the system stepwisely for controlled crystallization led to the formation of hollow, nanosized PE crystalline capsules, which are named as crystalsomes since they mimic the classical self-assembled structures such as liposome, polymersome and colloidosome. We show that the formation of the nanosized PE crystalsomes is driven by controlled crystallization at the curved liquid/liquid interface of the miniemulson droplet. The morphology, structure and mechanical properties of the PE crystalsomes were characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and atomic force spectroscopy. Electron diffraction showed the single-crystal-like nature of the crystalsomes. The incommensurateness between the nanocurved interface and the crystalline packing led to reduced crystallinity and crystallite size of the PE crystalsome, as observed from the X-ray diffraction measurements. Moreover, directly quenching the emulsion below the spinodal line led to the formation of hierarchical porous PE crystalsomes due to the coupling of the PE crystallization and liquid/liquid phase separation. We anticipate that this unique crystalsome represents a new type of nanostructure that might be used as nanodrug carriers and ultrasound contrast agents.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/cryst10080715
