CL-130987 Received: October 23, 2013 | Accepted: November 6, 2013 | Web Released: November 13, 2013 Highlight Review Layer-by-layer Nanoarchitectonics: Invention, Innovation, and Evolution Katsuhiko Ariga,*1,2 Yusuke Yamauchi,*1,3,4 Gaulthier Rydzek,1 QingminJi,1 Yusuke Yonamine,1,2 Kevin C.-W. Wu,5 and Jonathan P. Hill1,2 1World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA), National Institute for MaterialsScience (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 2Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 3Precursory Research for EmbryonicScience and Technology (PRESTO), Japan Science and Technology Agency (JST), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 4Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555 5Department of Chemical Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan (E-mail: [email protected], [email protected]) Katsuhiko Ariga is the Director of Supermolecules Group and Principal Investigator of World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA) at the National Institute for MaterialsScience (NIMS). He was born in 1962, and received his B.Eng., M.Eng., and Ph.D. Degrees from the Tokyo Institute of Technology (TIT). He was an Assistant Professor at TIT, worked as a postdoctoralfellow at the University of Texas at Austin, USA, and then served as a group leader in the Supermolecules Project at Japan Science and Technology (JST) agency. Thereafter, he worked as an Associate Professor at the Nara Institute of Science and Technology and then got involved with the ERATO Nanospace Project at JST. In January 2004, he moved to NIMS. His research field is based on supermolecular chemistry and surface science, including the boundary research areas of organic chemistry, physical chemistry, biochemistry, and materials chemistry. His major interests are the fabrication of novelfunctional nanostructures based on molecular recognition and self-assembly including Langmuir­Blodgett films, layer- by-layer films, and mesoporous materials. Dr. Ariga has become the fellow of Royal Society of Chemistry (FRSC) in 2013. Yusuke Yamauchi received his B.Eng. in 2003, M.Eng. in 2004, and Ph.D. degrees in 2007 from Waseda University in Japan. After receiving his Ph.D., he joined the National Institute for MaterialsScience (NIMS) as permanent staff. Then, he started his own research group “Inorganic materials laboratory” (http://www.yamauchi-labo.com). He concurrently serves as PRESTO Researcher of Japan Science and Technology Agency (JST), visiting professor at University of Wollongong (Australia) and TianjinUniversity (China), and visiting associate professor at Waseda University. He isalso an associate editor of APL Materials published by the American Institute of Physics (AIP), and an editorial board member of Scientific Reports published by the Nature Publishing Group. He has received many outstanding awards, such as the Young Scientists’ Prize of the Commendation for Science and Technology by MEXT in 2013, the PCCP Prize by the Royal Society of Chemistry in 2013, the Tsukuba Encouragement Prize in 2012, the Ceramic Society of Japan (CerSJ) Award in 2010, and the Inoue Research Award for Young Scientists in 2010. He has published more than 250 papers in international refereed journals. His major research interest istailored design of novel inorganic nanostructured materialswith various shapes and compositions toward practical applications. 36 | Chem. Lett. 2014, 43, 36–68 | doi:10.1246/cl.130987 © 2014 The Chemical Society of Japan Gaulthier Rydzek was introduced to research in 2008 at the University of Montreal (master study). He earned his Ph.D. in physical chemistry from the University of Strasbourg in 2012. Joining Prof.Ariga’s group at NIMS in 2013, he started working as a postdoctoral JSPS fellow. His current research interest includes surface chemistry and particularly the control of electroclick chemistry and electropolymerization. QingminJi earned her Ph.D. (2005) in chemistry from the University of Tsukuba. She started working as a postdoctoralfellow in National Institute for MaterialsScience (NIMS) from 2006 and became MANA scientist at World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA) in 2011. Her research currently focuses on the formation oflayer-by-layer films and the application of mesoporous structures for delivery systems. Yusuke Yonamine is a postdoctoral researcher in the Supermolecules Group, World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA), at the National Institute for MaterialsScience (NIMS). He received his Ph.D. degree from Tokyo Institute of Technology in 2010. Prior to working in NIMS, he worked as a postdoctoral researcher inUniversity of California, Irvine (2010­2012) and University of Michigan (2012­2013). His current interest is mechanical control of molecular machines at the air­ water interface. Kevin C.-W. Wu is currently an associate professor at the Department of Chemical Engineering, National Taiwan University (NTU), Taiwan. He was born in 1976, and received his Ph.D. degrees from The University of Tokyo, Japan it the year of 2005. From April 2005 to September 2006, he worked on the orientational control of 2D hexagonal mesoporous thin films with Prof. Kazuyuki Kuroda (Waseda University, Japan) as a post-doc. From October 2006 to July 2008, he joined Prof.Victor S.-Y. Lin’s group (Iowa State University, U.S.A.) as a post-doc. He returned to NTU and started his own research group in August 2008. His current interest is the synthesisof porous nanoparticles and thin films with desired structural orientation and functionalities for biomedical and energy-related applications. Jonathan P. Hill received his Ph.D. degree from Brunel University, U.K. in 1995. He is currently subgroup leader of the Supermolecules Group at the National Institute for Materials Science. Current research interests include synthesis and properties of tetrapyrroles and their supramolecular manifolds as well as unusual methods for preparing organic nanomaterials. Chem. Lett. 2014, 43, 36–68 | doi:10.1246/cl.130987 © 2014 The Chemical Society of Japan | 37 Abstract the novel concept of nanoarchitectonics,37­51 a technology system for arranging nanoscale structural units in a required Materials fabrication with nanoscale structural precision based configuration. This concept aims to produce new functionality of on bottom-up-type self-assembly has become more important l i i i i i i i i i li i i i l i i l a who eunt through concerted nteract ons w th n nanostruc- n var ous current d sc p nes n chem stry nc ud ng mater a s li l i l i f chemistry, organic chemistry, physical chemistry, analytical tures ke who e arch tectures. A though preparat on o new chemistry, biochemistry, colloid and surface chemistry, and materials based on nanoscaleself-assembly is an anticipated key supramolecular chemistry. Although the design of new materials concept in current technology, architecting whole three-dimen- based on nanoscaleself-assembly is anticipated as a key sional structures at nanoscale precision remains a difficult target i l i i l concept, prepar ng comp ete three-d mens ona structures at for current technologies. This should be the final goal but might nanoscale precision remains a difficult target using current l i i i not be an immediate target. Rather, dimension-reduced ap- techno og es. Rather, d mens on-reduced approaches such as l i i i l i layering of two-dimensional nanostructures into precisely proaches such as ayer ng two-d mens ona nanostructures nto controlled lamellar nanomaterials are currently achievable. In precisely controlled lamellar nanomaterials are currently achiev- particular, layer-by-layer (LbL) assembly is known as a highly able. This approach related to fabrication of ultrathin films plays versatile method for fabrication of controlled layered structures an important role in current technology because thin film f i i f i l i i l rom var ous k nds o component mater a susng very s mp e, preparation on certain surfaces isanimportant subject in inexpensive, and rapid procedures. Therefore, fabrication of l il fil i i connection with functional nanomaterials and artificial de- mu t ayer ms through the LbL depos t on process has ­ attracted growing interest from various research communities. vices.52 55 The high versatility and flexibility of LbL assembly is Various strategies such as the self-assembled monolayer continuously creating new concepts, new materials, new (SAM) method,56­63 Langmuir­Blodgett (LB) technique,64­71 procedures, and new applications. In thishighlight review, we l l l 72­94 i l f i i l f i i i l and ayer-by- ayer (LbL) assemb y have been w de y used ocus on nanoarch tecton cs by LbL assemb y. A ter an n t a f i fil i i l i introduction on the invention and a brief history of the LbL or th n m preparat on. In part cu ar, the LbL method s known assembly technique, innovations and the evolution of the as a highly versatile method for fabrication of controlled layered technique are described based mainly on recent examples, structures from various kinds of component materialsusing very which are categorized into two sections: (i) developments in simple, inexpensive, and rapid procedures (compared to other methodology (technical, material, and phenomenological aspects thin film processes). In thishighlight review, we focus on i i f ii i li i w th expans on o concept) and ( ) progress n app cat ons nanoarchitectonics with LbL assembly as the technological (physical, chemical/biochemical, and biomedical applications). concept which should be more widely established. Fabrication of multilayer films through an LbL deposition process has attracted growing interest from various research communities. f il li i f l 1. Introduction In act, the da y pub cat on rate or LbL-re ated research has reached more than three papers.