On-surface Synthesis
On-surface synthesis is an exciting new subfield in nanoscience that utilizes the catalyzing and templating roles of atomically flat substrates to perform chemical reactions. Suitable precursor molecules are commonly deposited onto such surfaces in ultra-high vacuum (UHV) conditions, after which they are (thermally) induced to react. The inherent two-dimensional nature of the substrate and consequent constrained motion of the molecules, combined with the clean conditions afforded by the UHV environment, allows for the construction of zero-, one- and two-dimensional nanostructures. Notable one-dimensional nanostructures that are now routinely produced using this methodology are graphene nanoribbons (GNRs). Graphene nanoribbons can sometimes also be "stitched together" to create nanoporous graphene, adding a whole new dimension to GNR research!
Together with the Chemistry group of Guangbin Dong, we have developed an exciting new technique to make graphene nanoribbons with exactly pre-defined length, structure, and shape.[1] Protecting-group Aided Iterative Synthesis works somewhat like building with legos: instead of making graphene nanoribbons by random polymerization, we can now build them up brick-by-brick, one monomer at the time. Since the electronic properties of nanoribbons are sensitively dependent on their structure, we can use PAIS to build many different functional electronic nanoribbon structures with atomic precision.
In our collaboration with the Nanoelectronics group of Jeffrey Bokor and the Theoretical Physics Group of Steven Louie, we have made a new type of material: chevron-type nanoporous graphene.[2] We built this material by stitching together molecules into one-dimensional chains, and subsequently fusing these chains together laterally in a twodimensional network that then becomes a nanoporous graphene. Upon fusion, the interfaces attain new electronic states not present in either the nanoribbons nor graphene. Recently, we have been able to make transistors from this exciting new material.[3] In a neat example of Feyman's envisioned superior performance of materials structurally controlled down to the atomic length scale (there is plenty of room at the bottom), our material outperforms "ordinary" graphene, the graphene nanoribbon "chains" it is composed of, and "top-down prepared" nanoporous graphene.
My collaborator Zafer Mutlu has since moved to the University of Arizona to start his own research group!
In our collaboration with the Chemistry group of Felix Fischer, we have developed a new method to synthesize atomically precise graphene nanoribbons.[4] Matrix-assisted direct (MAD) transfer is not restricted to either solution-based chemistry or on-surface synthesis, but rather takes the best of both worlds and even opens up new synthetic pathways, which vastly increases the scope of achievable GNR structures. Together with our recently established etching technique to transfer nanoribbons to field-effect transistor (FET) devices (see below), we have brought the fume hood (where the molecules are made) a lot closer to the microchip!
We have collaborated with the Nanoelectronics group of Jeffrey Bokor in developing new techniques to bring graphene nanoribbons from metallic surfaces to insulating ones.[5] After preparing crystalline gold thin films on top of an insulating surface, on-surface synthesis is used to create GNRs. Then, the gold layer is etched away as the nanoribbons settle in place on the surface underneath. The development is significant, since the GNR synthesis requires a metallic substrate yet the same metallic substrate prevents us to subsequently make nanoelectronic devices like GNR field-effect transistors (FETs). We can now use this technique to reliably bring GNRs on various different insulating surfaces and subject them to device fabrication and electrical measurements.
Publications
Programmable fabrication of monodisperse graphene nanoribbons via deterministic iterative synthesis. Jiangliang Yin, Peter H. Jacobse, Daniel Pyle, Ziyi Wang, Michael F. Crommie, Guangbin Dong, J. Am. Chem. Soc. 144 (2022)
Bottom-up Assembly of Nanoporous Graphene with Emergent Electronic States. Peter H. Jacobse, Ryan D. McCurdy, Jingwei Jiang, Daniel J. Rizzo, Gregory Veber, Paul Butler, Rafal Zuzak, Steven G. Louie, Felix R. Fischer, Michael F. Crommie, J. Am. Chem. Soc. 142 (2020)
Bottom-up Synthesized Nanoporous Graphene Transistors. Zafer Mutlu, Peter H. Jacobse, Ryan D. McCurdy, Juan P. Llinas, Yuxuan Lin, Gregory C. Veber, Felix R. Fischer, Michael F. Crommie, Jeffrey Bokor, Adv. Funct. Mater. 31 (2021)
Synergetic Bottom-Up Synthesis of Graphene Nanoribbons by Matrix-Assisted Direct Transfer. Ryan D. McCurdy, Peter H. Jacobse, Ilya Piskun, Gregory C. Veber, Daniel J. Rizzo, Rafal Zuzak, Zafer Mutlu, Jeffrey Bokor, Michael F. Crommie, Felix R. Fischer, J. Am. Chem. Soc. 143 (2021)
Transfer-Free Synthesis of Atomically Precise Graphene Nanoribbons on Insulating Substrates. Zafer Mutlu, Juan Pablo Llinas, Peter H. Jacobse, Ilya Piskun, Raymond Blackwell, Michael F. Crommie, Felix R. Fischer, Jeffrey Bokor, ACS Nano 15 (2021)
Structure and Local Variations of the Graphene Moiré on Ir(111). Sampsa K. Hämäläinen, Mark P. Boneschanscher, Peter H. Jacobse, Ingmar Swart, Katariina Pussi, Wolfgang Moritz, Jouko Lahtinen, Peter Liljeroth, Jani Sainio, Phys. Rev. B 201406 (2013)
One Precursor but Two Types of Graphene Nanoribbons: On-Surface Transformations of 10,10′-Dichloro-9,9′-bianthryl on Ag(111). Peter H. Jacobse, Konstantin A. Simonov, Mark J. J. Mangnus, Gleb I. Svirskiy, Alexander V. Generalov, Alexander S. Vinogradov, Anders Sandell, Nils Mårtensson, Alexei B. Preobrajenski, Ingmar Swart, J. Phys. Chem. C 123 (2019)
Tracking on-surface Chemistry with Atomic Precision. Peter H. Jacobse, Marc-Etienne Moret, Robertus J. M. Klein Gebbink, Ingmar Swart, Synlett 28 (2017)
Electronic Components Embedded in a Single Graphene Nanoribbons. Peter H. Jacobse, Amina Kimouche, Tim Gebraad, Mikko M. Ervasti, Joseph M. Thijssen, Peter Liljeroth, Ingmar Swart, Nat. Commun. 8 (2017)
Precursor Geometry Determines the Growth Mechanism in Graphene Nanoribbons. Fabian Schulz, Peter H. Jacobse, Filippo Federici Canova, Joost van der Lit, David Z. Gao, Adrianus van den Hoogenband, Patrick Han, Robertus J. M. Klein Gebbink, Marc-Etienne Moret, Pekka M. Joensuu, Ingmar Swart, Peter Liljeroth, J. Phys. Chem. C 121 (2017)
Aryl Radical Geometry Determines Nanographene Formation on Au(111). Peter H. Jacobse, Adrianus van den Hoogenband, Marc-Etienne Moret, Robertus J. M. Klein Gebbink, Ingmar Swart, Angew. Chem. Int. Ed. 55 (2016)
Graphene Nanoribbons: From fume hood to transistor. Peter H. Jacobse, Utrecht University Repository (Dissertation) (2018)