Abstract

After decades of developments, electron microscopy has become a powerful and irreplaceable tool in understanding the ionic, electrical, mechanical, chemical, and other functional performances of next-generation polymers and soft complexes. The recent progress in electron microscopy of nanostructured polymers and soft assemblies is important for applications in many different fields, including, but not limited to, mesoporous and nanoporous materials, absorbents, membranes, solid electrolytes, battery electrodes, ion- and electron-transporting materials, organic semiconductors, soft robotics, optoelectronic devices, biomass, soft magnetic materials, and pharmaceutical drug design. For synthetic polymers and soft complexes, there are four main characteristics that differentiate them from their inorganic or biomacromolecular counterparts in electron microscopy studies: (1) lower contrast, (2) abundance of light elements, (3) polydispersity or nanomorphological variations, and (4) large changes induced by electron beams. Since 2011, the Center for Nanophase Materials Sciences (CNMS) at Oak Ridge National Laboratory has been working with numerous facility users on nanostructured polymer composites, block copolymers, polymer brushes, conjugated molecules, organic–inorganic hybrid nanomaterials, organic–inorganic interfaces, organic crystals, and other soft complexes. This review crystalizes some of the essential challenges, successes, failures, and techniques during the process in the past ten years. It also presents some outlooks and future expectations on the basis of these works at the intersection of electron microscopy, soft matter, and artificial intelligence. Machine learning is expected to automate and facilitate image processing and information extraction of polymer and soft hybrid nanostructures in aspects such as dose-controlled imaging and structure analysis.

Highlights

  • Electron microscopy has been of continued interest for decades, playing vital roles in revealing micro- and nanostructures as well as functionality relationships in traditional and novel materials

  • It is well known that electron microscopy of synthetic polymers has very different expectations and challenges than that of proteins, DNAs, and other biomacromolecules with monodispersity

  • Two older [7,8] and two newer reviews [6,9] summarized the progress in electron microscopy of synthetic polymers and organic materials over the years

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Summary

Introduction

Electron microscopy has been of continued interest for decades, playing vital roles in revealing micro- and nanostructures as well as functionality relationships in traditional and novel materials. Traditionally including four major industrial categories (adhesives, elastomers, coatings, and fibers), have intriguing structures that are often hierarchical in nature and span from the nano- to micrometer scales [1]. Synthetic polymers and their small molecule counterparts such as organic crystals and amorphous or crystalline oligomers, as well as their interfaces and composite complexes with inorganic materials, find their impacts well around us in applications such as energy storage, energy harvesting, ion and electron transport, sensors, and medicines [1,2,3,4,5]. Machine learning is expected to automate and facilitate image processing and information extraction of polymer and soft hybrid nanostructures in aspects such as dose-controlled imaging and soft structure analysis

Comparison of Various Nanostructure Characterization Techniques
Probes
Connecting Real and Reciprocal Space
Sample Preparation Based on Contrast Mechanism
Plunge Freezing
To Stain or Not to Stain
Sample Drifting
Electron Dose and Spatial Resolution
Bright Field and High Resolution
Diffraction
Chemical Mapping with Monitored Electron Damage
Other Low-Dose Techniques and Temporal Resolution
Morphological Variations and Hierarchical Structures
Polymer-Based Solar Cells
Organic Semiconductors
Energy Storage
Polymer Electrolyte
Battery Interfaces
Macromolecular Medicine
Self-Assembly and Kinetics of Block or Graft Copolymers
Self-Assembly and Kinetics of Biomacromolecules
Small Molecule Drugs
10. Outlook
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