Developments in Direct Nanopatterning of Graphene; Towards Direct Write.

Developments in direct nanopatterning of graphene; Towards direct write. Szymon Abrahamczyk* Ondřej Sakreida Alicja Bachmatiuk Gražyna Simha Martynková Mark H. Rümmeli* Dr. Szymon Abrahamczyk EBEAM Centre, CNT, CEET, VŠB TUO, Ostrava, 708 00, Czechia Email Address: [email protected] Prof. Dr. Mark H. Rümmeli EBEAM Centre, CNT, CEET, VŠB TUO, Ostrava, 708 00, Czechia The Leibniz Institute for Solid State and Materials Research Dresden (IFW Dresden), Helmholtzstr. 20, Dresden, D-01069, Germany Soochow Institute for Energy and Materials InnovationS (SIEMIS), Optoelectronics and Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, and Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province, School of Energy, Soochow University, Suzhou, 215006, China. Email Address: [email protected] Ing. Ondřej Sakreida EBEAM Centre, CNT, CEET, VŠB TUO, Ostrava, 708 00, Czechia Prof. Dr. Alicja Bachmatiuk EBEAM Centre, CNT, CEET, VŠB TUO, Ostrava, 708 00, Czechia Faculty of Chemistry, Wroclaw University of Science and Technology, Wybrzeze Wyspiarskiego 27, Wroclaw 50-370, Poland Prof. Gražyna Simha Martynková Nanotechnology Centre, CEET, VŠB-TUO, 708 33, Czechia Keywords: Graphene Nanopatterning, Focused Electron Beam-Induced Deposition (FEBID), Laser-Induced Graphitisation, Direct Write, Focused Ion Beam Milling (FIBM), Polymer-to-Graphene Conversion (P2G), Gas Injection System (GIS) Abstract Graphene, with its exceptional electronic, mechanical, and thermal properties, remains a cornerstone material for next-generation nanoelectronics. However, conventional lithographic approaches to graphene patterning are fraught with challenges, including contamination, alignment complexity, and scalability constraints. This review critically examines the evolving landscape of direct-write graphene technologies, focusing on forefront strategies such as focused electron beam-induced deposition (FEBID), polymer-tographene (P2G) conversion, focused ion beam (FIB) modification, and laser-assisted graphitisation. These techniques represent a departure from traditional top-down or transfer-based methods by enabling bottomup, spatially resolved patterning without intermediary masking steps. Particular attention is devoted to the physicochemical mechanisms that underlie electronand photon-mediated graphitisation, the role of precursor chemistry and substrate interactions, as well as the influence of beam parameters on sp2-carbon content and structural ordering. The review further delineates the limitations intrinsic to current methodologies, including partial graphitisation, resolution fidelity, and hardware constraints, and proposes a roadmap to achieve truly ’direct’ graphene writing. This includes in situ processing under controlled environments, advanced beam control systems, and the adoption of catalytic and graphitisable precursors. Collectively, this work provides a comprehensive foundation for the rational design of next-generation nanofabrication protocols and underscores the transformative potential of direct-write techniques in enabling scalable, high-fidelity graphene-based devices. 1 1 Introduction 1.1 What is graphene? Graphene was first confirmed and isolated as a stable free-standing structure by Novoselov et al. in 2004 using the famous Scotch tape method.[1–3] This marked the beginning of the ’gold rush’ in graphene research has exploded in physics, materials science and engineering, leading to extensive studies on its applications in electronics, nanotechnology, and energy storage.[4, 5] The non-exhaustive list of notable developments would include advanced synthesis techniques such as chemical vapour deposition (CVD), epitaxial growth on SiC, pyrolysis, liquid phase exfoliation (LPE), polymer-to-graphene conversion (P2G), reduction of graphene oxide etc. [6], elucidation of the electronic and quantum properties of graphene (graphene transistors, quantum effects, high-frequency electronics)[7], introduction into materials science and engineering (composites, energy storage, thermal management)[8] and biomedical and environmental applications (biosensors, drug delivery, water filtration and desalination)[9]. Graphene’s unique structure confers remarkable properties, including high electrical conductivity, mechanical strength, and thermal stability, making it ideal for nanotechnology applications.[2] A single pristine layer of graphene (SLG) is a zero-bandgap material allowing a conduction of massless Dirac fermions making it an excellent conductor with electrical conductivity of around 105S m−1, comparable to that of metallic silver in bulk approx. 6.2 ×107S m−1.[2, 10] The deterioration of the conductivity of metals in nanoscale due to quantum size effects and surface scattering of the electrons (down to < 104S m−1) provides single layer pristine graphene a significant benefit for application in nanometric-scale electronics as a conductor.[11, 12] However, this advantage is highly dependent on the quality and fabrication method of the graphene used. The quality of graphene often refers to the number of layers, the presence of defects, the chemical uniformity, and the size of the graphene domain.[13, 14] For example, a double layer graphene has an order of magnitude lower electrical conductivity (104S m−1) than that of SLG.[15] While in SLG the conduction (CB) and valence bands (VB) are touching at a single Dirac point, the graphene bilayer exhibits interlayer interactions (van der Waals and π−πspin-orbit coupling) in effect creating a finite bandgap (< 0.2 eV), making the electrons behave much more as particles with an effective mass.[16] Further stacking and defects will also affect the conductivity of the synthesised graphene, making this material difficult to process.[17– 19]Graphene defects are typically classified into several types: point defects such as vacancies[21, 24], interstitial defects, substitutions[25–27], or adatoms[28]; line defects such as grain boundaries[29] and dislocations[22, 29]; plane defects such as multilayer regions, folds, and wrinkles[30]; structural distortions, including Stone-Wales defects[31], ripples, and corrugations; and chemical and functional defects such as oxidised and hydrogenated areas, as well as edge defects[20]. These dopants and defect states will significantly affect the electronic structure of graphene and introduce a band gap.[13, 32] Figure 1 illustrates how this doping might appear in a graphene sheet. These, depending on the situation, can be considered as unwanted defects that deteriorate the quality of graphene, or dopants that make graphene a material with a highly tuneable bandgap.[13, 33] Chemical doping can be introduced into graphene by incorporating heteroatoms (B[34], N[34–36], P[37, 38], O[39], S[40], F[41], Cl[42, 43], Al[27], Co[44], H[45, 46], Si) into the graphene lattice that donate or accept electrons, functionalisation of graphene (oxidation to rGO) that disrupts the graphene’s sp2 hybridisation, or even adsorption of metal atoms, particles, or even moleculae that would transfer their charge to the graphene surface. The chemical doping gives a lot of control over the type and degree of doping, allowing bandgap tuning from 0 - 2.9 eV. However, structural changes such as single or multiple vacancies that allow for chemical homogeneity are not currently difficult to introduce with controlled processes. These can alter the electronic properties of graphene by the introduction of strains, rotations, and lattice mismatches. [47] The last but not least type of graphene quality parameter is its graphene domain size. Small graphene domains have significantly orders of magnitude lower carrier mobilities as a result of phonons and impurity scattering contributing to resistivity, whereas in large graphene domains the transport is more 2 1.2 Timeline of graphene fabrication methods Figure 1: A) Simplified chemical structure of a graphene sheet, and examples of possible doping/defect states. All the image have a white scale bar representing 2 nm. The edge effect, point vacancy, and multiple vacancy TEM images are reproduced from Warner et al.[20], Robertson et al.[21], and Lehtinen et al.[22], respectively. B) Recognised processes used for graphene fabrication. Interpretation of similar figures from citations [23] and [17]. ballistic.[1] The small domains domains below 10 nm can even experience quantum confinement effects shifting the Dirac cone to opening a bandgap.[48] Furthermore, the alignment and orientation of graphene domains, especially in polycrystalline films, can lead to the formation of grain boundaries and twisting between domains, significantly impacting both charge mobility and structural strength. Depending on the twist angle, these twisted domains can display moiré superlattice patterns, giving rise to novel electronic effects, including flat bands and correlated insulating phases, as seen in twisted bilayer graphene. Consequently, producing large-area, single-crystal graphene is crucial for high-performance electronic and optoelectronic applications. These monocrystalline graphene sheets reduce grain boundary scattering and maintain graphene’s inherent properties, such as its extremely high carrier mobility and linear band structure. Significant effort has been invested in refining CVD methods to manage nucleation density and growth kinetics, enabling centimetre-scale single-crystal domains. The quality of graphene can be quantified using multitechnique approach combining structural characterisation (Raman spectroscopy, TEM and AFM), electrical properties (4-point probe, Kelvin probe and cAFM), chemical purity and dopant quantification (XPS, FTIR and TGA). Figure 2 shows the different stages of graphitisation of organic, carbon-rich materials. These changes can be monitored as a change in the line shape of a Raman spectrum, as can be seen further in Figure 3. In amorphous carbon, the bands are very broad, the 2D peak is usually not onset, and the positions of the peaks also differ. In graphitic material, the full width at half-maxima (FWHM) of the G and 2D bands becomes much sharper. For few-layer graphene, interpreting the deconvolution of the G, D, and 2D bands allows for quality assessment. 1.2 Timeline of graphene fabrication methods Although the term ‘graphene’ gained prominence in the early 2000s, theoretical interest in its properties dates back to mid-20th century. For instance, Wallace predicted in 1947 its unique band structure, and Semenoff in 1984 described the massless Dirac fermion behaviour of electrons in graphene.[50, 51] Since its first isolation by Geim and Novoselov in 2004, graphene has driven advances in a wide range of fields, 3 1.2 Timeline of graphene fabrication methods Figure 2: A schematic representation of degree of graphitisation. Recreated from the graphic abstract by Schuepfer et al.[49] from electronics to nanotechnology.[1, 3, 5] The past two decades have allowed for the development of advanced synthesis techniques. Current graphene fabrication procedures can be divided into various groups, including exfoliation (physical, chemical, or mechanical etc.), decomposition of organic materials (catalytic or non-catalytic), chemical reduction of graphene oxide (GO) into reduced GO (rGO) or epitaxial growth (CVD).[17] Graphene fabrication methods are usually segregated into bottom-up and top-down approaches, as was done by Yan et al. and Wu et al.[17, 23] For the purpose of this review, the graphene fabrication techniques were segregated into bulk graphene fabrication (exfoliation), film growth (CVD, PVD) and direct graphene writing (with laser, electrons etc.) as lustrated in the Figure 1. 1.2.1 Graphene fabrication from bulk materials Fabrication of graphene often entails the breakdown of bulk graphite into individual graphene layers or small stacks, which distinguishes it markedly from bottom-up approaches that synthesise graphene from molecular precursors or carbon-rich materials. Among bulk graphene fabrication strategies, exfoliation is predominant and encompasses mechanical, chemical, and liquid-phase methods. Table 1 contains summary of the key exfoliation techniques used to fabricate bulk graphene. The most iconic example is mechanical exfoliation via the "Scotch tape method", first used by Novoselov et al. to isolate pristine monolayer graphene, an achievement that later earned the Nobel Prize in Physics (2010).[1, 2] Although this method remains the benchmark for producing defect-free monolayers, its lack of scalability limits its industrial applicability.[52] In contrast, chemical exfoliation introduces intercalating agents, such as acids or alkali metals, to expand the interlayer spacing within graphite, followed by sonication to yield graphene sheets.[53–55] This approach, often used in the reduction of graphene oxide (GO), is scalable but typically introduces a high density of structural defects, necessitating further post-treatment. Liquid phase exfoliation (LPE), another scalable route, disperses graphite in solvents under sonication to overcome van der Waals interactions.[56–58] The surface energy of the solvent must be carefully matched with that of graphene to maintain stable dispersions and prevent reaggregation.[59, 60] While these exfoliation techniques have facilitated the integration of graphene into commercial products, they still suffer from critical limitations, including poor control over domain size, number of layers, and defect density. Moreover, patterning of graphene fabricated using these methods is nearly exclusively possible by lithography, lift-off or precise transfer. 4 1.3 Graphene processing and patterning limitations Table 1: Summary of exfoliation techniques used to fabricate bulk graphene. Exfoliation Quality Applications Pros Cons References Scotch tape method Pristine monolayers, large domains, minimal defects Fundamental research, transistors, quantum devices Highest quality graphene, ideal for research Low yield, not scalable, manual process [1, 2] LPE Small flakes, variable defects, few-layer graphene Coatings, composites, inks, energy storage Scalable, cost-effective, solution-processable High defect density, solvent contamination [56–60] Chemical graphene oxide reduction High defect density, oxidized, reduced conductivity Bulk graphene oxide, energy applications, membranes Large-scale production, inexpensive Reduces electrical properties, requires post-treatment [61–63] Electrochemical Moderate defect density, few-layer graphene Flexible electronics, supercapacitors Environmentally friendly, scalable Difficult thickness control, lower quality than mechanical [64–66] Intercalationassisted Layer-by-layer exfoliation, lower defects Battery electrodes, printed electronics Selective exfoliation, controlled quality Requires specialized chemicals, limited scalability [67, 68] 1.2.2 Film growth Graphene may also be synthesised directly on a substrate, a process commonly known as bottom-up growth. Graphene synthesis via bottom-up methodologies primarily involves the incorporation of carbon atoms into the graphene lattice through surface-catalysed chemical processes. A widely adopted method is chemical vapour deposition (CVD), in which gaseous carbon sources like methane or acetylene disintegrate on catalytic metallic surfaces such as copper or nickel, facilitating the production of high-quality monolayer graphene. This technique offers substantial control over the layer count, crystallinity, and domain size of the graphene films produced.[17] Some new approaches in CVD also implement polymer-to-graphene conversion, in which a thin film of a polymer (most often PMMA) is deposited onto a substrate from solution.[69, 70] The film is then converted into graphene with the help of elevated temperature (> 800 ◦C), application of reducing agent (H2and Ar gas mix ) and catalysts (Cu, Ni, Cr[71]). Factors such as the temperature of the substrate, the deposition rate, and the type of metal catalyst employed play roles in determining the quality and number of graphene layers formed. For example, Wu et al. indicate that Cu substrates are conducive to the growth of single-layer graphene due to their low carbon solubility, while nickel tends to produce multiple layers through carbon dissolution and precipitation upon cooling. Epitaxial growth on SiC substrates yields high-quality, wafer-scale graphene with excellent crystallinity and minimal defects, but it is hindered by its high cost and limited scalability due to substrate constraints and the need for ultra-high temperatures (>1200 ◦C).[72] Pyrolysis of carbon-rich materials, particularly polymer precursors, provides a facile, transfer-free route towards direct graphene formation on various substrates, and it can be spatially confined for patterning, but it suffers from limited structural control and a higher degree of disorder, making it less suitable for electronic-grade applications. [73, 74] Collectively, while epitaxy ensures quality, CVD balances quality and scalability, and pyrolysis offers simplicity and integration versatility at the expense of structural precision. 1.3 Graphene processing and patterning limitations The commercialisation of graphene-based electronic devices has been hindered by a series of fabrication and scalability challenges. Chief among these is the reliance on conventional lithographic processes, which often involve multiple steps, such as masking, etching, and transfer, which introduce defects, contamination, or alignment issues, particularly when aiming for nanoscale precision or heterogeneous integration[77]. Moreover, high-performance device fabrication commonly requires the synthesis of uniform large-area monolayer graphene via CVD, a process constrained by high temperatures, specific substrate compatibility, and limited patterning capabilities[69, 78]. These limitations collectively reduce throughput and increase production costs. 5 Figure 3: A) SEM image and a Raman spectrum of graphene grown using epitaxial growth on SiC.[75] B) HRTEM image and Raman spectrum of a graphene obtained as a result of pyrolysis of green tea extract at 1100 ◦C.[74] C) SEM image and a Raman spectrum oF a monolayer graphene sheet grown using CVD and transferred onto Si.[76] All Raman spectra were reproduced and digitised from plots in the citations [74–76] Numerous attempts have been made to improve the processability of graphene, one of which involves poly(acrylonitrile) (PAN) as a transfer medium.[79] The study investigates the use of PAN as a transfer medium for wafer-scale graphene. The authors found that PAN can effectively serve as a transfer medium, simultaneously facilitating the encapsulation and transfer of large-area graphene films. This approach addresses common issues in graphene transfer processes, such as contamination and mechanical damage, thereby improving the quality and scalability of graphene-based applications.[79] Transferred graphene would still need to be patterned in conventional ways. An innovative technique called Thermal, Electrical, and Water Assisted Reaction (TEAWAR) facilitates the transformation of polymethyl methacrylate (PMMA) and similar organic residues into graphene.[80] The TEAWAR process leverages the synergistic effects of thermal energy, electrical stimulation, and water mediation to achieve this conversion. This approach offers a novel pathway for graphene synthesis, potentially enhancing the efficiency and sustainability of graphene production from polymeric materials. Attempts to create graphene-rich inks for 3D printing were reviewed by Jiang et al. The review outlines recent developments in 3D printing of graphene-based materials and their applications in energy storage and conversion devices and discusses the extrusion-based direct ink writing technique, emphasising the rheological behaviour of graphene oxide (GO) dispersions and strategies for preparing printable GO inks. The review highlights how 3D printing enables the design of advanced electrode architectures, potentially improving the performance of energy storage devices.[8] This methodology, however does not align with the scope of this review and graphene-ink based additive manufacturing methods will not be considered further. 6 Figure 4: Venn diagram showing various advantages shred between EBL, CVD, Additive manufacturing (AM) with electron beam induced deposition sharing all these. The processes are also summarised as diagrams where CVD was recreated from Esmaeilpour et al.[81] and AM fromManokruang[82]. 2 Focused electron beam induced deposition (FEBID) 2.1 Fundamentals of electron-material interactions Focused electron beam-induced deposition (FEBID) relies on intricate interactions between the electron beam and, for example, reactive gas, thin films, and even substrates, to transform materials and deposit it directly and in controlled mannner on a nanoscale. These processes resemble the ones occuring during electron beam lithography (EBL) which has similar modus operandi, thus both of these research areas use similar approaches and terminology. Both primary electrons (PE) and secondary electrons (SE), as well as substrate-mediated effects, play critical roles in these material transformations. PEs, typically generated at voltages between 0.1–30 kV, penetrate the substrate and lose energy via inelastic collisions, generating cascades of secondary electrons (SEs) with energies usually below 50 eV. These SEs are largely responsible for the surface-localised dissociation of precursor molecules in FEBID due to their highly localised energy deposition. Higher energy PEs result in broader interaction volumes, whereas lower accelerationvoltages confine the effect near the surface. Backscattered electrons (BSEs), more prominent on high-atomicnumber substrates such as Cu or Ni, contribute to a lateral broadening of the deposition area.[83] In parallel, electron-induced ionisation leads to radiolysis, where precursor bonds can be cleaved to form radicals and volatile species such as CO, CO2, and H2O. The amount of electron radiation required to achieve the material transformation, called dose (D) is defined as: D=1 AZt 0 i(t)dt where A is area, t is time, and i is current. Typically in EBL, this dose is a representation of the minimal value at which the resist (usually polymer) transforms by bond cleavage, or cross-linking. At high 7 2.2 Separation into graphitisable and non-graphitisable materials doses, this residual carbon can transition into amorphous or sp2-rich carbon domains, setting the stage for graphene-like structures. For conversion of polymer to graphene (P2G) these values are expected to be much higher than for EBL as the reaction end is expected not as initial transformation but rather as complete graphitisation. IIn FEBID, this value indicates the amount of radiation needed to convert the gaseous precursor and deposit the solid onto a substrate e.g. by the removal of ligands from the precursor which makes it volatile or bond cleavage and formation of radicals that reassemble and deposit as solid.[84, 85] Although knock-on displacement typically requires electron energies above 80–100 keV—beyond the range of standard SEM-based EBID—lighter atoms like hydrogen and oxygen may still be displaced, contributing to the purification of the deposit. Substrate properties also significantly influence the process: conductive substrates (e.g., Cu, Ni, doped Si) dissipate charge and often catalyse graphitisation, whereas insulating substrates (e.g., SiO2, glass) can accumulate charge, leading to beam distortion. Variable pressure conditions with inert gases may help mitigate charging without interfering chemically. Substrate atomic number affects BSE yield and, consequently, the spatial extent of deposition. Importantly, catalytic substrates such as Cu can aid carbon atom diffusion and reorganisation, facilitating higher-quality graphene growth. Collectively, the combination of SE-driven dissociation, radiolytic decomposition, selective knockon displacement, and catalytic substrate interaction would drive the success of EBID in forming graphene nanostructures. 2.2 Separation into graphitisable and non-graphitisable materials The separation of graphitisable and non-graphitisable materials is a fundamental concept in carbon material science, particularly relevant to the fabrication of graphene and other graphitic structures.[86] Upon thermal treatment, carbon-rich precursors exhibit divergent structural transformations depending on their molecular structure and bonding characteristics. Graphitisable materials, such as certain pitches and polycyclic aromatic hydrocarbons and certain polymers, undergo structural reordering upon heating, eventually forming crystalline graphene layers with high stacking order and extended lateral dimensions. This transition is facilitated by the absence of cross-linking side groups and a high degree of aromaticity, allowing carbon atoms to rearrange into the thermodynamically favourable graphitic lattice. In contrast, non-graphitisable materials, PMMA, possess a cross-linked, amorphous structure due to the presence of heteroatoms and functional groups such as hydroxyls. These groups hinder the alignment and growth of ordered graphene layers, resulting in materials that remain largely disordered even at elevated temperatures. The distinction between these two classes of materials could be particularly significant in the context of electron beam processing, where the structural predisposition of the precursor determines the feasibility and quality of graphitisation, with direct implications for the electronic, optical and mechanical properties of the resulting carbon films.[86, 87] It seems that the vast majority of research on polymer-to-graphene conversion is influenced by the research on electron beam lithography on PMMA as a resist material.[88] 2.3 Polymer-to-graphene (P2G) conversion using electron beam EBID enables the direct transformation of polymeric precursors into graphenic materials through a combination of radiolytic and thermal effects.[89] Upon e-beam irradiation, the polymer matrix undergoes ionization and bond scission, producing free radicals that recombine to form a cross-linked, carbon-rich network. Simultaneously, dehydrogenation and deoxygenation expel heteroatoms such as hydrogen, oxygen, and nitrogen, enriching the sp²-carbon content. Polymers like PMMA, polystyrene, PAN, polyimides, and phenolic resists (e.g., SU-8 or AZ5214) display distinct responses under EBID, influenced by their molecular structure. For instance, PMMA carbonizes into amorphous features, while PAN undergoes electroninduced cyclization, mimicking thermal stabilisation and yielding nitrogen-doped graphenic carbon.[88, 90, 91] Polyimides, rich in heteroatoms, can form porous, conductive graphite foams under high-dose irradiation.[92] Beyond chemical changes, the e-beam also induces localised heating via inelastic scattering, facilitating pyrolysis and bond reconfiguration. Substrate effects further influence this process; conductive metals like Cu or Ni not only dissipate heat but also catalyse dehydrogenation and induce planarisation. 8 2.4 Electron beam induced modifications in SAMs Figure 5: A) The process flow diagram of the e-beam lithographic process for the fabrication of graphene nanostructures on copper substrate. Low-quality graphene was formed at step 3, and the high-quality graphene at step 6. B) Raman spectra of the sample at the different preparation stages Recreated from Bi et al.[88] Post-irradiation annealing—typically at 300–800 ◦C in inert or reducing atmospheres—significantly enhances structural ordering and conductivity, driving the reorganisation of disordered carbon into graphitic domains. While EBID alone often yields amorphous or turbostratic carbon, sustained irradiation or thermal treatment promotes graphitisation, especially in the presence of catalytic substrates. The final material typically comprises nanocrystalline graphite or a mosaic of small graphene domains, with resistivities ranging from 10−4to 10−3Ωcm, which are sufficient for use in microelectrodes, sensors, and other functional carbon nanostructures. Thus, EBID offers a controllable, lithography-compatible method for bottom-up fabrication of graphenic nanomaterials, with tunable properties governed by precursor chemistry, electron dose, and thermal conditions. 2.4 Electron beam induced modifications in SAMs Electron beam-induced modifications in self-assembled monolayers (SAMs) offer a powerful and versatile approach for tailoring surface chemistry and nanoscale patterning with high spatial resolution. Upon exposure to low-energy electron irradiation, typically below 100 eV, SAMs undergo a variety of physico-chemical transformations, including bond cleavage, desorption, cross-linking, and reorientation of molecular backbones. In particular, SAMs featuring carboxylic acid (CA) anchoring groups on coinage metal substrates such as silver have demonstrated pronounced susceptibility to electron-induced reactions. These modifications are driven by electron-stimulated cleavage of the carboxylate–metal bond, leading to partial or complete desorption of molecules, followed by the formation of a carbonaceous residue via cross-linking of the remaining organic fragments. The presence of aromatic backbones in CA-based SAMs enhances the propensity for cross-linking due to delocalised π-electrons, enabling the conversion of the monolayer into a robust, insoluble carbon nanomembrane. Furthermore, electron irradiation can induce significant conformational and orientational changes in the SAMs, such as reorientation or disordering of the molecular packing. These effects are highly dependent on the molecular structure, packing density, and energy and dose of the electron beam. Such controlled modifications are increasingly exploited in applications ranging from lithography and surface patterning to the fabrication of chemically and mechanically stable nanostructures[94–96] 9 and edge sharpness. The environmental chamber, though indispensable for in situ gas-phase reactions or pressure-regulated processes, introduces complications in electron scattering and beam stability, thereby requiring precise regulation of chamber pressure and gas composition to mitigate image degradation and ensure beam fidelity. The GIS, a critical enabler for introducing carbonaceous precursors or forming gas, can pose contamination risks if not finely calibrated, potentially leading to undesirable carbon deposition on non-targeted areas or even optical components such as electron lenses etc.. Additionally, the incorporation of a heating stage, essential for post-irradiation conversion or catalytic enhancement, demands thermal isolation and robust material compatibility to prevent off-gassing or structural warping under prolonged heating cycles. Importantly, the BSD detector, often situated close to the sample chamber, is vulnerable to contamination from volatilised precursors or beam-induced sputtering in gas-rich environments. Prolonged exposure to reactive gases, especially under elevated temperatures and electron bombardment, can degrade detector sensitivity or induce fouling on sensitive components, including scintillators or photomultiplier tubes. Proper shielding, controlled gas flow paths, and regular maintenance schedules become imperative to protect detector integrity and overall instrument longevity. These multifaceted constraints underscore the necessity of carefully orchestrated hardware configurations and operational protocols to enable reliable, reproducible, and truly "direct" graphene writing in SEM platforms. 6 Future Work Emerging directions in FEBID and LIG for graphene patterning reflect a confluence of technological innovation and sustainability considerations. Low-dose precursor-to-graphene strategies are being explored for patterning on flexible substrates, such as those used in paper-based electronics, enabling lightweight and disposable graphene-based devices. Hybrid workflows that integrate electron beam lithography with chemical vapour deposition (CVD) offer promising avenues for spatially selective doping, enhancing functionality at the nanoscale. The implementation of machine-learning algorithms to optimise beam patterning parameters is poised to significantly improve precision, throughput, and reproducibility simultaneously being able to avoid proximity effects, drifts etc. Concurrently, the development and deployment of environmentally benign precursors are gaining traction, driven by the imperative for sustainable and less hazardous e-beam processing protocols. Furthermore, the field is witnessing a growing interest in the identification and classification of graphitisable materials suitable for electron beam-induced deposition (EBID) of graphene. This necessitates a revised framework to guide the rational selection of precursors based on their structural evolution under electron irradiation. Acknowledgements All authors thank the European Union’s Horizon Europe research and innovation programme under the grant agreement No. 101087143 (Electron Beam Emergent Additive Manufacturing (EBEAM)) M.H.R. thanks for funding from the National Natural Science Foundation of China (Grant No. 52071225) References (1) K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva and A. A. Firsov, Science, 2004, 306, Publisher: American Association for the Advancement of Science, 666–669. (2) A. K. Geim and K. S. Novoselov, Nature Materials, 2007, 6, Publisher: Nature Publishing Group, 183–191. (3) S. Ganguly and J. Sengupta, Discover Nano, 2024, 19, 110. (4) T. Radsar, H. Khalesi and V. Ghods, Optical and Quantum Electronics, 2021, 53, 178. (5) S. Kang, J. Chang, J. Lim, D. J. Kim, T.-S. Kim, K. C. Choi, J. H. Lee and S. Kim, Nature Communications, 2024, 15, Publisher: Nature Publishing Group, 8288. (6) H.-K. Seo and T.-W. 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