AFM, SPM, STM and TEM Techniques: Brilliant Techniques in Characterization of Block Copolymer Self-Assembly Nanostructures G. Mir Mohamad Sadeghi 1 and Mahsa Sayaf 2 1 AMIRKABIR University of technology, Dep. polymer engineering and color technology, 15875-4413, Tehran, Iran 2 ISFAHAN University of technology, Chemical engineering faculty, Isfahan, Iran Techniques such as AFM, SPM, ATM and TEM will be discussed in this chapter. At first principles of techniques will be presented. Then a short summary about how to use these techniques to characterize self-assembly nanostructures based on block copolymers. Thin film morphology of semicrystalline BCPs and control of the thin film morphology through crystallization-related technologies could be studied by AFM. For example a fingerprint-like pattern, with a domain spacing of ~40 nm could be seen for polystyrene-b-poly (4-vinylpyridine) by using of SPM height and phase images of a thin film ~47 nm in thickness after annealing in solvent. Some example about using of the techniques will be presented. Keywords: Self-Assembly; Block copolymers; Nanostructures; SPM; AFM; TEM; Characterization 1. Block copolymer self-assembly nanostructures 1.1 Block copolymers Block copolymers are useful in many applications where a number of different polymers are connected together to yield a material with hybrid properties. For example, thermoplastic elastomers are block copolymers containing a rubbery matrix (polybutadiene or polyisoprene) and glassy hard domains (often polystyrene). The block copolymer, a kind of polymer alloy, behaves as a rubber at ambient conditions, but can be molded at high temperatures due to the presence of the glassy domains that act as physical cross-links. In solution, attachment of a water-soluble polymer to an insoluble polymer leads to the formation of micelles in amphiphilic block copolymers. The presence of micelles leads to structural and flow characteristics of the polymer in solution that differ from either parent polymer. A block copolymer molecule contains two or more polymer chains attached at their ends. Linear block copolymers comprise two or more polymer chains in sequence, whereas a star block copolymer comprises more than two linear block copolymers that are attached at a common branch point. Polymers containing at least three homopolymers attached at a common branching point have been termed mixed arm block copolymers, although they can also be viewed as multigraft copolymers. Some binary and ternary block copolymer architectures are showing in Fig. 1 and Fig.2. Binary block copolymers Ternary block copolymers Microscopy: advances in scientific research and education (A. Méndez-Vilas, Ed.) __________________________________________________________________ 591 © FORMATEX 2014