Two‐Photon Polymerization: Fundamentals, Materials, and Chemical Modification Strategies

Two‐photon polymerization (TPP) has become a premier state‐of‐the‐art method for microscale fabrication of bespoke polymeric devices and surfaces. With applications ranging from the production of optical, drug delivery, tissue engineering, and microfluidic devices, TPP has grown immensely in the past two decades. Significantly, the field has expanded from standard acrylate‐ and epoxy‐based photoresists to custom formulated monomers designed to change the hydrophilicity, surface chemistry, mechanical properties, and more of the resulting structures. This review explains the essentials of TPP, from its initial conception through to standard operating principles and advanced chemical modification strategies for TPP materials. At the outset, the fundamental chemistries of radical and cationic polymerization are described, along with strategies used to tailor mechanical and functional properties. This review then describes TPP systems and introduces an array of commonly used photoresists including hard polyacrylic resins, soft hydrogel acrylic esters, epoxides, and organic/inorganic hybrid materials. Specific examples of each class—including chemically modified photoresists—are described to inform the understanding of their applications to the fields of tissue‐engineering scaffolds, micromedical, optical, and drug delivery devices. This review describes the fundamentals of two‐photon polymerization (TPP) along with chemical modification strategies of TPP materials applied to medical devices, optics, cell biology, and drug delivery systems.