Spatially resolved fluoroalkylation and alkylation of graphene by direct laser writing.

Two classes of photoactive compounds containing fluoroalkyl- and alkyl silver carboxylates were utilized for graphene laser writing, affording a set of patterned graphene architectures bearing various functionalities. The laser patterning of graphene is accomplished by using laser-triggered decomposition of silver carboxylates to generate radicals confined to the irradiated area for the selective binding of graphene.

Synergistic Combination of Reductive Covalent Functionalization and Atomic Layer Deposition-Towards Spatially Defined Graphene-Organic-Inorganic Heterostructures.

Three-dimensionally (3D) well-ordered and highly integrated graphene hybrid architectures are considered to be next-generation multifunctional graphene materials but still remain elusive. Here, we report the first realization of unprecedented 3D-patterned graphene nano-ensembles composed of a graphene monolayer, a tailor-made structured organophenyl layer, and three metal oxide films, providing the first example of such a hybrid nano-architecture. These spatially resolved and hierarchically structured quinary hybrids are generated via a two-dimensional (2D)-functionalization-mediated atomic layer deposition growth process, involving an initial lateral molecular programming of the graphene lattice via lithography-assisted 2D functionalization and a subsequent stepwise molecular assembly in these regions in the z-direction. Our breakthrough lays the foundation for the construction of emerging 3D-patterned graphene heterostructures.

Spatially Resolved Janus Patterning of Graphene by Direct Laser Writing.

Covalently patterned Janus-functionalized graphene featuring a spatially defined asymmetric bifacial addend binding motif remains a challenging synthetic target. Here, a facile and universal laser writing approach for a one-step covalent Janus patterning of graphene is reported, leading to the formation of up to now elusive graphene architectures, solely consisting of antaratopically functionalized superlattices. The structurally defined covalent functionalization procedure is based on laser-triggered concurrent photolysis of two different photosensitizers situated on both sides of the graphene plane, generating radicals and subsequent addend binding in the laser-irradiated areas only. Careful structure analysis was performed by Raman spectroscopy and Kelvin probe force microscopy. In terms of the advantages of our newly established concept, including a simple/easy-to-operate patterning procedure, arbitrary pattern availability, and a high degree of addend binding, an easy access to tailor-designed Janus-functionalized graphene devices with spatially resolved functional entities can be envisaged.

Molecular Stacking on Graphene.

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.

Carbon Nano-onions: Potassium Intercalation and Reductive Covalent Functionalization.

Herein we report the synthesis of covalently functionalized carbon nano-onions (CNOs) via a reductive approach using unprecedented alkali-metal CNO intercalation compounds. For the first time, an in situ Raman study of the controlled intercalation process with potassium has been carried out revealing a Fano resonance in highly doped CNOs. The intercalation was further confirmed by electron energy loss spectroscopy and X-ray diffraction. Moreover, the experimental results have been rationalized with DFT calculations. Covalently functionalized CNO derivatives were synthesized by using phenyl iodide and n-hexyl iodide as electrophiles in model nucleophilic substitution reactions. The functionalized CNOs were exhaustively characterized by statistical Raman spectroscopy, thermogravimetric analysis coupled with gas chromatography and mass spectrometry, dynamic light scattering, UV-vis, and ATR-FTIR spectroscopies. This work provides important insights into the understanding of the basic principles of reductive CNOs functionalization and will pave the way for the use of CNOs in a wide range of potential applications, such as energy storage, photovoltaics, or molecular electronics.

Evolution of Graphene Patterning: From Dimension Regulation to Molecular Engineering.

The realization that nanostructured graphene featuring nanoscale width can confine electrons to open its bandgap has aroused scientists' attention to the regulation of graphene structures, where the concept of graphene patterns emerged. Exploring various effective methods for creating graphene patterns has led to the birth of a new field termed graphene patterning, which has evolved into the most vigorous and intriguing branch of graphene research during the past decade. The efforts in this field have resulted in the development of numerous strategies to structure graphene, affording a variety of graphene patterns with tailored shapes and sizes. The established patterning approaches combined with graphene chemistry yields a novel chemical patterning route via molecular engineering, which opens up a new era in graphene research. In this review, the currently developed graphene patterning strategies is systematically outlined, with emphasis on the chemical patterning. In addition to introducing the basic concepts and the important progress of traditional methods, which are generally categorized into top-down, bottom-up technologies, an exhaustive review of established protocols for emerging chemical patterning is presented. At the end, an outlook for future development and challenges is proposed.

Hypervalent Iodine Compounds as Versatile Reagents for Extremely Efficient and Reversible Patterning of Graphene with Nanoscale Precision.

Rational patterning and tailoring of graphene relies on the disclosure of suitable reagents for structuring the target functionalities on the 2D-carbon network. Here, a series of hypervalent iodine compounds, namely, 1-chloro-1,2-benziodoxol-3(1H)-one, 1,3-dihydro-1-hydroxy-3,3-dimethyl-1,2-benziodoxole, and 3,3-dimethyl-1-(trifluoromethyl)-1,2-benziodoxole is reported to be extremely efficient for a diversified graphene patterning. The decomposition of these compounds generates highly reactive Cl, OH, and CF3 radicals exclusively in the irradiated areas, which subsequently attach onto the graphene leading to locally controlled chlorination, hydroxylation, and trifluoromethylation, respectively. This is the first realization of a patterned hydroxylation of graphene, and the degrees of functionalization of the patterned chlorination and trifluoromethylation are both unprecedented. The usage of these mild reagents here is reasonably facile compared to the reported methods using hazardous Cl2 or ICl and allows for sophisticated pattern designs with nanoscale precision, promising for arbitrary nanomanipulation of graphene's properties like hydrophilicity and conductivity by the three distinct functionalities (Cl, OH, and CF3 ). Moreover, the attachment of functional entities to these highly functionalized graphene nanoarchitectures is fully reversible upon thermal annealing, enabling a full writing/storing/reading/erasing control over the chemical information stored within graphene. This work provides an exciting clue for target 2D functionalization and modulation of graphene by using suitable hypervalent iodine compounds.

A general concept for highly efficient covalent laser patterning of graphene based on silver carboxylates.

Three novel types of spatially resolved graphene architectures GA, GB, and GC respectively bearing CH3-, C6H5- and C3F7 groups are efficiently constructed by newly developed laser-writing concepts using silver carboxylates as corresponding photosensitizers. These 2D-structured samples are unequivocally characterized by Raman spectroscopy and SEM-EDS.

Covalent 2D Patterning, Local Electronic Structure and Polarization Switching of Graphene at the Nanometer Level.

A very facile and efficient protocol for the covalent patterning and properties tuning of graphene is reported. Highly reactive fluorine radicals were added to confined regions of graphene directed by laser writing on graphene coated with 1-fluoro-3,3-dimethylbenziodoxole. This process allows for the realization of exquisite patterns on graphene with resolutions down to 200 nm. The degree of functionalization, ranging from the unfunctionalized graphene to extremely high functionalized graphene, can be precisely tuned by controlling the laser irradiation time. Subsequent substitution of the initially patterned fluorine atoms afforded an unprecedented graphene nanostructure bearing thiophene groups. This substitution led to a complete switch of both the electronic structure and the polarization within the patterned graphene regions. This approach paves the way towards the precise modulation of the structure and properties of nanostructured graphene.

Molecular embroidering of graphene.

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.

Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts.

Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, 31 P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well as electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction.

Direct Laser Writing on Graphene with Unprecedented Efficiency of Covalent Two-Dimensional Functionalization.

Laser writing as a simple and straightforward method for covalent 2D patterning of graphene remains challenging. Here, we report a facile and efficient approach for a laser-induced 2D patterning of graphene utilizing silver trifluoroacetate, providing an unprecedented high degree of functionalization. The use of laser-triggered photolysis of silver trifluoroacetate to generate trifluoromethyl radicals, confined only to the laser-irradiated region, leads to the selective reaction of graphene, thereby completing direct laser writing on graphene toward a spatially resolved 2D-patterned architecture. This highly 2D-functionalized graphene is completely reversible. Furthermore, a more complex patterned graphene hybrid architecture was constructed, taking advantage of the simultaneously produced/patterned silver nanoparticles during the laser-writing process. Considering the simplicity of this approach and its ability to provide high degrees of functionalization, the prerequisite of 2D patterning of other 2D materials based on this method is provided.

Covalent 2D-Engineering of Graphene by Spatially Resolved Laser Writing/Reading/Erasing.

We report a facile and efficient method for the covalent 2D-patterning of monolayer graphene via laser irradiation. We utilized the photo-cleavage of dibenzoylperoxide (DBPO) and optimized the subsequent radical additions to non-activated graphene up to that level where controlled covalent 2D-patterning of graphene initiated by spatially resolved laser writing is possible. The covalent 2D-functionalization of graphene, which is monitored by scanning Raman microscopy (SRM) is completely reversible. This new concept enables write/read/erase control over the covalent chemical information stored on the graphene surface.

Covalently Doped Graphene Superlattices: Spatially Resolved Supratopic- and Janus-Binding.

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.

Quantifying the Covalent Functionalization of Black Phosphorus.

A straightforward quantification method to consistently determine the overall functionalization degree of covalently modified two-dimensional (2D) black phosphorus (BP) by Raman spectroscopy has been carried out. Indeed, the successful reductive methylation of the BP lattice using sodium intercalation compounds and exhibiting different functionalization degrees has been demonstrated by 31 P-magic angle spinning (MAS) NMR spectroscopy. Furthermore, the correlation of 31 P-MAS NMR spectroscopy and statistical Raman spectroscopy (SRS) revealed the first method to determine the functionalization degree of BP solely by evaluating the intensities of distinct peaks in the Raman spectra of the covalently modified material, in a similar way to the widely employed ID /IG ratio of graphene research.

Recent Advances in Graphene Patterning.

As an emerging field of research, graphene patterning has received considerable attention because of its ability to tailor the structure of graphene and the respective properties, aiming at practical applications such as electronic devices, catalysts, and sensors. Recent efforts in this field have led to the development of a variety of different approaches to pattern graphene sheets, providing a multitude of graphene patterns with different shapes and sizes. These established patterning techniques in combination with graphene chemistry have paved the road towards highly attractive chemical patterning approaches, establishing a very promising and vigorously developing research topic. In this review, an overview of commonly used strategies is presented that are categorized into top-down and bottom-up routes for graphene patterning, focusing mainly on new advances. Other than the introduction of basic concepts of each method, the advantages/disadvantages are compared as well. In addition, for the first time, an overview of chemical patterning techniques is outlined. At the end, the challenges and future perspectives in the field are envisioned.

Few-layer Black Phosphorous Catalyzes Radical Additions to Alkenes Faster than Low-valence Metals.

The substitution of catalytic metals by p-block main elements has a tremendous impact not only in the fundamentals but also in the economic and ecological fingerprint of organic reactions. Here we show that few-layer black phosphorous (FL-BP), a recently discovered and now readily available 2D material, catalyzes different radical additions to alkenes with an initial turnover frequency (TOF0) up to two orders of magnitude higher than representative state-of-the-art metal complex catalysts at room temperature. The corresponding electron-rich BP intercalation compound (BPIC) KP6 shows a nearly twice TOF0 increase with respect to FL-BP. This increase in catalytic activity respect to the neutral counterpart also occurs in other 2D materials (graphene vs. KC8) and metal complex catalysts (Fe0 vs. Fe2- carbon monoxide complexes). This reactive parallelism opens the door for cross-fertilization between 2D materials and metal catalysts in organic synthesis.

Mechanical cleaning of graphene using in situ electron microscopy.

Avoiding and removing surface contamination is a crucial task when handling specimens in any scientific experiment. This is especially true for two-dimensional materials such as graphene, which are extraordinarily affected by contamination due to their large surface area. While many efforts have been made to reduce and remove contamination from such surfaces, the issue is far from resolved. Here we report on an in situ mechanical cleaning method that enables the site-specific removal of contamination from both sides of two dimensional membranes down to atomic-scale cleanliness. Further, mechanisms of re-contamination are discussed, finding surface-diffusion to be the major factor for contamination in electron microscopy. Finally the targeted, electron-beam assisted synthesis of a nanocrystalline graphene layer by supplying a precursor molecule to cleaned areas is demonstrated.

Spatially Resolved Bottom-Side Fluorination of Graphene by Two-Dimensional Substrate Patterning.

Patterned functionalization can, on the one hand, open the band gap of graphene and, on the other hand, program demanding designs on graphene. The functionalization technique is essential for graphene-based nanoarchitectures. A new and highly efficient method was applied to obtain patterned functionalization on graphene by mild fluorination with spatially arranged AgF arrays on the structured substrate. Scanning Raman spectroscopy (SRS) and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS) were used to characterize the functionalized materials. For the first time, chemical patterning on the bottom side of graphene was realized. The chemical nature of the patterned functionalization was determined to be the ditopic scenario with fluorine atoms occupying the bottom side and moieties, such as oxygen-containing groups or hydrogen atoms, binding on the top side, which provides information about the mechanism of the fluorination process. Our strategy can be conceptually extended to pattern other functionalities by using other reactants. Bottom-side patterned functionalization enables utilization of the top side of a material, thereby opening up the possibilities for applications in graphene-based devices.