Search

The sequential vertical polyfunctionalization of 2D addend‐patterned graphene is still elusive. Here, we report a practical realization of this goal via a “molecular building blocks” approach, which is based on a combination of a lithography‐assisted reductive functionalization approach and a post‐functionalization step to sequentially and controllably link the molecular building blocks ethylpyridine, cis‐dichlorobis(2,2′‐bipyridyl)ruthenium, and triphenylphosphine (4‐methylbenzenethiol, respectively) on selected lattice regions of a graphene matrix. The assembled 2D hetero‐architectures are unambiguously characterized by various spectroscopic and microscopic measurements, revealing the stepwise stacking of the molecular building blocks on the graphene surface. Our method overcomes the current limitation of a one‐layer‐only binding to the graphene surface and opens the door for a vertical growth in the z‐direction.

Efficiently assembling heterostructures with desired interface properties, stability, and facile patternability is challenging yet crucial to modern device fabrication. Here, we demonstrate an interface coupling concept to bottom-up construct covalently linked graphene/MoS

Efficiently assembling heterostructures with desired interface properties, stability, and facile patternability is challenging yet crucial to modern device fabrication. Here, we demonstrate an interface coupling concept to bottom-up construct covalently linked graphene/MoS2 heterostructures in a spatially defined manner. The covalent heterostructure domains are selectively created in analogy to the traditional printmaking technique, enabling graphic patterns at the bottom MoS2 layer to be precisely transferred to the top graphene layer. This bottom-up connection and transcription of chemical information is achieved simply via laser beam irradiation. Our approach opens up a new paradigm for heterostructure construction and integration. It enables the efficient generation and real-time visualization of spatially well-resolved covalent graphene/MoS2 heterostructures, facilitating further design and integration of patterned heterostructures into new generations of high-performance devices.

Patterned graphene‐functionalization with a tunable degree of functionalization can tailor the properties of graphene. Here, we present a new reductive functionalization approach combined with lithography rendering patterned graphene‐functionalization easily accessible. Two types of covalent patterning of graphene were prepared and their structures were unambiguously characterized by statistical Raman spectroscopy together with scanning electron microscopy/energy‐dispersive X‐ray spectroscopy (SEM‐EDS). The reversible defunctionalization processes, as revealed by temperature‐dependent Raman spectroscopy, enable the possibility to accurately modulate the degree of functionalization by annealing. This allows for the management of chemical information through complete write/store/erase cycles. Based on our strategy, controllable and efficient patterning graphene‐functionalization is no longer a challenge and facilitates the development of graphene‐based devices., Writing on graphene: Patterned graphene functionalization with a tunable degree of functionalization was achieved by using a reductive protocol combined with lithography. The structures were unambiguously confirmed by statistical Raman spectroscopy and SEM‐EDS. Based on this strategy, controllable and patterned graphene functionalization is no longer a challenge, which facilitates the development of graphene‐based devices.

Structured covalent two-dimensional patterning of graphene with different chemical functionalities constitutes a major challenge in nanotechnology. At the same time, it opens enormous opportunities towards tailoring of physical and chemical properties with limitless combinations of spatially defined surface functionalities. However, such highly integrated carbon-based architectures (graphene embroidery) are so far elusive. Here, we report a practical realization of molecular graphene embroidery by generating regular multiply functionalized patterns consisting of concentric regions of covalent addend binding. These spatially resolved hetero-architectures are generated by repetitive electron-beam lithography/reduction/covalent-binding sequences starting with polymethyl methacrylate covered graphene deposited on a Si/SiO2 substrate. The corresponding functionalization zones carry bromobenzene-, deutero-, and chloro-addends. We employ statistical Raman spectroscopy together with scanning electron microscopy/energy dispersive X-ray spectroscopy for an unambiguous characterization. The exquisitely ordered nanoarchitectures of these covalently multi-patterned graphene sheets are clearly visualized., Covalently 2D-patterning graphene with different chemical functionalities is an attractive way to tailor its physical and chemical properties. Here, the authors realize spatially defined 2D-hetereoarchitectures of graphene via a strategy of molecular embroidering.

Amongst the different existing methods to passivate black phosphorus (BP) from environmental degradation, the noncovalent functionalization with perylene diimides (PDI) has been postulated as one of the most promising routes because it allows preserving its electronic properties. This work describes the noncovalent functionalization and outstanding environmental protection of BP with tailor made PDI having peri-amide aromatic side chains, which include phenyl and naphthyl groups, exhibiting a significantly increased molecule-BP interaction. These results are rationalized by density functional theory (DFT) calculations showing that the adsorption energies are mainly governed by van der Waals (vdW) interactions and increase concomitantly with the aromatic character of the side chains. The resulting hybrids are thoroughly characterized showing enhanced ambient and thermal stabilities. Last but not least, hybrid organic-inorganic BP-PDI field effect transistors (FETs) are studied for the first time showing the usefulness of PDI derivatives as efficient passivation layers while obtaining improved values of electron mobilities. These results pave the way for the use of optimized PDIs by molecular engineering to preserve the electronic properties of BP FETs, using straightforward wet chemical approaches.

Rational design and fabrication of graphene nanoarchitectures with multifunctionality and multidimensionality remains quite a challenge. Here, we present a synthetic sequence, based on the combination of two advanced patterned-functionalization principles, namely, laser-writing and poly(methyl methacrylate) (PMMA)-assisted lithographic processes, leading to unprecedented covalently doped graphene superlattices. Spatially resolved supratopic- and Janus-binding were periodically weaved on the graphene sheet, leading to four different types of zones with distinct chemical doping and structural properties. Notably, this is also the first realization of patterned Janus graphene. The elaborate chemical doping with micrometer resolution is unequivocally evidenced by scanning Raman spectroscopy (SRS) and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS). The design of the pattern as well as the degree of chemical doping on both opposite sides of graphene can be easily manipulated, rendering exciting potential for graphene nanosystems.

We study photoluminescence (PL) of MoS2 monolayers in optical cavities that can be tuned in operando. Technically, we use the recently developed squeezable nanojunction (SNJ). It is a versatile mechanical setup that has been useful to study thermoelectric effects at electronic tunneling distances. Here, we emphasize on a cavity with 0–3 micrometer distance with optical access. Due to the tunable cavity, we see strong distortions of PL spectra. By an analysis of the ensemble, we identify a normalization protocol that gives access to disentangling the contributions from excitation, gating and emission. The systematic evolution of data reconfirms the drastic influence of the local electromagnetic mode budget on the spectral properties. The experiment further underscores the broadband application range of the SNJ technique, able for combining (nano-) electronic functionality with optical access and a tunable light-matter interface.

The development of an efficient method to patterning 2D MoS2 into a desired topographic structure is of particular importance to bridge the way towards the ultimate device. Herein, we demonstrate a patterning strategy by combining the electron beam lithography with the surface covalent functionalization. This strategy allows us to generate delicate MoS2 ribbon patterns with a minimum feature size of 2 μm in a high throughput rate. The patterned monolayer MoS2 domain consists of a spatially well‐defined heterophase homojunction and alternately distributed surface characteristics, which holds great interest for further exploration of MoS2 based devices., The patterned 2D MoS2 surface was achieved through covalent functionalization of electron beam lithography (EBL) defined guiding areas. The patterned MoS2 surface displays switchable surface characteristics in a spatially defined manner, confirmed by scanning Raman spectroscopy and PL mapping, which may hold great promise for the development of state‐of‐the‐art electronic and optoelectronic devices.