Self-Assembled Two-Dimensional Heteromolecular Nanoporous Molecular Arrays on Epitaxial Graphene

Karmel, Hunter J.; Chien, TeYu; Demers-Carpentier, Vincent; Garramone, J. J.; Hersam, Mark C.

doi:10.1021/jz4025518

Cited by 18 publications

(30 citation statements)

References 53 publications

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“…Similar PTCDI/melamine networks have been subsequently prepared on Au/mica [88], epitaxial graphene [89], highly-oriented pyrolytic graphite (HOPG), hexagonal boron nitride and molybdenum disulphide by deposition of the molecular building blocks from solution [90]. Besides the use of two molecules having complementary recognition sites, also molecules exhibiting self-complementary groups like carboxylic groups are of great interest.…”

Section: Molecular Self-assembly and Porous Networkmentioning

confidence: 99%

Confinement properties of 2D porous molecular networks on metal surfaces

Müller

Enache

Stöhr

2016

J. Phys.: Condens. Matter

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Quantum effects that arise from confinement of electronic states have been extensively studied for the surface states of noble metals. Utilizing small artificial structures for confinement allows tailoring of the surface properties and offers unique opportunities for applications. So far, examples of surface state confinement include thin films, artificial nanoscale structures, vacancy and adatom islands, self-assembled 1D chains, vicinal surfaces, quantum dots and quantum corrals. In this review we summarize recent achievements in changing the electronic structure of surfaces by adsorption of nanoporous networks whose design principles are based on the concepts of supramolecular chemistry. Already in 1993, it was shown that quantum corrals made from Fe atoms on a Cu(1 1 1) surface using single atom manipulation with a scanning tunnelling microscope confine the Shockley surface state. However, since the atom manipulation technique for the construction of corral structures is a relatively time consuming process, the fabrication of periodic two-dimensional (2D) corral structures is practically impossible. On the other side, by using molecular self-assembly extended 2D porous structures can be achieved in a parallel process, i.e. all pores are formed at the same time. The molecular building blocks are usually held together by non-covalent interactions like hydrogen bonding, metal coordination or dipolar coupling. Due to the reversibility of the bond formation defect-free and long-range ordered networks can be achieved. However, recently also examples of porous networks formed by covalent coupling on the surface have been reported. By the choice of the molecular building blocks, the dimensions of the network (pore size and pore to pore distance) can be controlled. In this way, the confinement properties of the individual pores can be tuned. In addition, the effect of the confined state on the hosting properties of the pores will be discussed in this review article.

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Section: Molecular Self-assembly and Porous Networkmentioning

confidence: 99%

Confinement properties of 2D porous molecular networks on metal surfaces

Müller

Enache

Stöhr

2016

J. Phys.: Condens. Matter

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“…Several groups have studied the process of molecular self‐assembly on graphene in the real space by scanning tunneling microscopy . These studies often focused epitaxial graphene grown onto metallic or semiconducting SiC surfaces, and recently also on graphene transferred onto insulating SiO 2 or BN …”

Section: Molecular Assembly In Hybrid Van Der Waals Heterostructures:mentioning

confidence: 99%

“…While in several cases the molecular assembly and its properties represent the main focus of STM studies, only a few reports address the effects of a given molecular assembly on the electronic properties of 2DMs . In these cases, an STM study of the molecular assembly on a 2DM (typically graphene) is combined to the investigation of the electrical properties of the same system, addressed at the macroscopic level (for instance, in devices).…”

Section: Molecular Assembly In Hybrid Van Der Waals Heterostructures:mentioning

confidence: 99%

“…The interactions of molecular layers with the inert surface of 2DM are mediated by vdW forces analogous to those between different inorganic sheets, so that similar interface effects can be envisaged in both cases, making organic/inorganic architectures the hybrid equivalent of fully inorganic vdWHs. The analogy is even more profound if one considers that crystalline molecular monolayers can be obtained on 2DMs that can be integrated in complex multilayered heterostructures composed of alternating organic/inorganic single layers.…”

Section: Introductionmentioning

confidence: 99%

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When 2D Materials Meet Molecules: Opportunities and Challenges of Hybrid Organic/Inorganic van der Waals Heterostructures

2018

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van der Waals heterostructures, composed of vertically stacked inorganic 2D materials, represent an ideal platform to demonstrate novel device architectures and to fabricate on-demand materials. The incorporation of organic molecules within these systems holds an immense potential, since, while nature offers a finite number of 2D materials, an almost unlimited variety of molecules can be designed and synthesized with predictable functionalities. The possibilities offered by systems in which continuous molecular layers are interfaced with inorganic 2D materials to form hybrid organic/inorganic van der Waals heterostructures are emphasized. Similar to their inorganic counterpart, the hybrid structures have been exploited to put forward novel device architectures, such as antiambipolar transistors and barristors. Moreover, specific molecular groups can be employed to modify intrinsic properties and confer new capabilities to 2D materials. In particular, it is highlighted how molecular self-assembly at the surface of 2D materials can be mastered to achieve precise control over position and density of (molecular) functional groups, paving the way for a new class of hybrid functional materials whose final properties can be selected by careful molecular design.

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“…Similar assemblies have been replicated on weakly coupled graphene to obtain nano-porous networks and use them in the so-called "host-guest" architectures. For example, sequential deposition of PTCDI and the 3-fold symmetric molecule melamine has been used to form hexagonal network stabilized by intermolecular hydrogen bonds on G/SiC [110]. Hexagonal porous network stabilized by hydrogen bonds have also been realized by 3-fold symmetric tricarboxylic acids e.g., trimesic acid (TMA) and benzene-tribenzoic acid (BTB), which have been studied in detail on graphite and noble metal surfaces [111].…”

Section: Molecular Templatesmentioning

confidence: 99%

Molecular assembly on two-dimensional materials

Kumar¹,

Banerjee²,

Liljeroth³

2017

Nanotechnology

106

108

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Molecular self-assembly is a well-known technique to create highly functional nanostructures on surfaces. Self-assembly on two-dimensional (2D) materials is a developing field driven by the interest in functionalization of 2D materials in order to tune their electronic properties. This has resulted in the discovery of several rich and interesting phenomena. Here, we review this progress with an emphasis on the electronic properties of the adsorbates and the substrate in well-defined systems, as unveiled by scanning tunneling microscopy (STM). The review covers three aspects of the self-assembly. The first one focuses on non-covalent self-assembly dealing with site-selectivity due to inherent moiré pattern present on 2D materials grown on substrates. We also see that modification of intermolecular interactions and molecule-substrate interactions influences the assembly drastically and that 2D materials can also be used as a platform to carry out covalent and metal-coordinated assembly. The second part deals with the electronic properties of molecules adsorbed on 2D materials. By virtue of being inert and possessing low density of states near the Fermi level, 2D materials decouple molecules electronically from the underlying metal substrate and allow high-resolution spectroscopy and imaging of molecular orbitals. The moiré pattern on the 2D materials causes site-selective gating and charging of molecules in some cases. The last section covers the effects of self-assembled, acceptor and donor type, organic molecules on the electronic properties of graphene as revealed by spectroscopy and electrical transport measurements. Non-covalent functionalization of 2D materials has already been applied for their application as catalysts and sensors. With the current surge of activity on building van der Waals heterostructures from atomically thin crystals, molecular self-assembly has the potential to add an extra level of flexibility and functionality for applications ranging from flexible electronics and OLEDs to novel electronic devices and spintronics. * This is slightly expanded version of the review published in Nanotechnology 28(2017), 082001

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Self-Assembled Two-Dimensional Heteromolecular Nanoporous Molecular Arrays on Epitaxial Graphene

Cited by 18 publications

References 53 publications

Confinement properties of 2D porous molecular networks on metal surfaces

Confinement properties of 2D porous molecular networks on metal surfaces

When 2D Materials Meet Molecules: Opportunities and Challenges of Hybrid Organic/Inorganic van der Waals Heterostructures

Molecular assembly on two-dimensional materials

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