Weak mismatch epitaxy and structural Feedback in graphene growth on copper foil

Review: 46 refs.

The growth of graphene has been carried out on cube‐textured (100) oriented Cu (CTO‐Cu) foils using chemical vapor deposition (CVD). Well‐aligned triangular grains self‐assembled on CTO‐Cu during CVD heating in flowing hydrogen. The nucleation of triangular graphene grains has been confirmed. This demonstrates that the shape and possible alignment of the graphene grains can potentially be tuned by changing the properties of the substrate, which should ultimately lead to improved electrical properties of the graphene. This type of graphene nucleation and alignment is novel and has not been observed in previous studies on other copper foil samples.

We investigated the nucleation and grain growth of graphene grown on Cu through radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) at different temperatures. A reasonable shielding method for the placement of copper was employed to achieve graphene by RF-PECVD. The nucleation and growth of graphene grains during PECVD were strongly temperature dependent. A high growth temperature facilitated the growth of polycrystalline graphene grains with a large size (~ 2 μm), whereas low temperature induced the formation of nanocrystalline grains. At a moderate temperature (790 to 850 °C), both nanocrystalline and micron-scale polycrystalline graphene grew simultaneously on Cu within 60 s with 50 W RF plasma power. As the growth time increased, the large graphene grains preferentially nucleated and grew rapidly, followed by the nucleation and growth of nanograins. There was competition between the growth of the two grain sizes. In addition, a model of graphene nucleation and grain growth during PECVD at different temperatures was established.

Graphene, the atomic thin carbon film with honeycomb lattice, holds great promise in a wide range of applications, due to its unique band structure and excellent electronic, optical, mechanical, and thermal properties. Scientists are researching this star material because of the development of various emerging preparation techniques, among which chemical vapor deposition (CVD) has received the fastest advances in the past few years. For the CVD growth of graphene, the ultimate goal is to achieve the highest quality in the largest scale and lowest cost with a precise control of layer thickness, stacking order, and crystallinity. To meet this goal, researchers need a comprehensive understanding and effective controlling of the growth process, especially to its elementary steps. In this Account, we focus on our recent progresses toward the controlled surface growth of graphene and its two-dimensional (2D) hybrids via rational designs of CVD elementary processes, namely, process engineering. A typical CVD process consists of four main elementary steps: (A) adsorption and catalytic decomposition of precursor gas, (B) diffusion and dissolution of decomposed carbon species into bulk metal, (C) segregation of dissolved carbon atoms onto the metal surface, and finally, (D) surface nucleation and growth of graphene. Absence or enhancement of each elementary step would lead to significant changes in the whole growth process. Metals with certain carbon solubility, such as nickel and cobalt, involve all four elementary steps in a typical CVD process, thus providing us an ideal system for process engineering. The elementary segregation process can be completely blocked if molybdenum is introduced into the system as an alloy catalyst, yielding perfect monolayer graphene almost independent of growth parameters. On the other hand, the segregation-only process of predissolved solid carbons is also capable of high-quality graphene growth. By using a synergetic Cu-Ni alloy, we are able to further enhance the control to such a segregation technique, especially for the thickness of graphene. By designing a cosegregation process of carbon atoms with other elements, such as nitrogen, doped graphene could be synthesized directly with a tunable doping profile. Copper with negligible carbon solubility provides another platform for process engineering, where both carbon dissolution and segregation steps are negligible in the CVD process. Carbon atoms decomposed from precursors diffuse on the surface and build up the thermodynamically stable honeycomb lattice. As a result, graphene growth on copper is self-limited, and formation of multilayer graphene is generally prohibited. Being able to control this process better, as well as the high quality produced, makes copper-based growth the dominating synthesis procedure in the graphene community. We designed a two-temperature zone system to spatially separate the catalytic decomposition step of carbon precursors and the surface graphitization step for breaking this self-limited growth feature, giving high-quality Bernal stacked bilayer graphene via van der Waals epitaxy. We performed the so-called wrinkle engineering by growing graphene on nanostructured copper foil together with a structure-preserved surface transfer. In such a way, we controlled the wrinkling or folding on graphene and further fabricated graphene nanoribbon arrays by self-masked plasma etching. Moreover, by designing a two-step patching growth process on copper, we succeeded in synthesizing the mosaic graphene, a patchwork of intrinsic and nitrogen-doped graphene connected by single crystalline graphene p-n junctions. By following a general concept of process engineering, our work on the designed CVD growth of graphene and its 2D hybrids provides a unique insight of this research field. It enables the precise growth control of graphene together with the in-depth understanding of CVD growth process, which would further stimulate the pace of graphene applications.

化学气相沉积法(CVD)在制备高质量、大尺寸石墨烯方面显示出巨大 的优势 [11~13] , 该方法成本低廉, 更能够和目前的集 成 电 路 工 艺 相 兼 容 .

In this research, we have investigated the unintended graphene nucleation problem and its damaging effects on monolayer graphene synthesis in low-pressure chemical vapor deposition (LPCVD) process. This problem is the growth of graphene on the copper surface with no carbon feedstock. A new source of undesired carbon species was identified which has not been addressed so far. The hydrogen-rich heating stage was diagnosed as the onset of the unintended nucleation for the first time owing to the determinant catalytic role of hydrogen in this stage. It was found out that this problem leads to uncontrollable growth of multilayer graphene, growth of defective graphene film and also inhibition of the reliable synthesis of monolayer graphene. We managed to grow enhanced-quality monolayer graphene by developing some innovative solutions to the problem containing a general solution based on the hydrogen effects in the heating stage. The results reveal a significant decrease in the unintended nucleation density from ∼2000 to almost zero domains per 100 × 100 μm2 copper area. Furthermore, Raman, HRTEM and SAED analysis confirm the defect-free growth of monolayer graphene after employing the solutions. These findings could pave the way for the reliable synthesis of high-quality monolayer graphene as well as large-sized graphene domains.

A simply and reproducible way is proposed to significantly suppress the nucleation density of graphene on the copper foil during the chemical vapor deposition process. By inserting a copper foil into a tube with one close end, the nucleation density on the copper foils can be reduced by more than five orders of magnitude and an ultra-low nucleation density of ~10 nucleus/cm2 has been achieved. The structural analyses demonstrate that single crystal monolayer graphene with a lateral size of 1.9 mm can be grown on the copper foils under the optimized growth condition. The electrical transport studies show that the mobility of such single crystal graphene is around 2400 cm2/Vs.

Transfer-free growth of polymer-derived graphene on dielectric substrate from mobile hot-wire-assisted dual heating system

Since its discovery in 2004, graphene has boosted numerous fundamental sciences and technological applications due to its massless Dirac particle-like linear band dispersion, that causes unprecedented physical properties. Among the various methods for synthesizing graphene, chemical vapor deposition is the most suitable approach for scalable production on a wafer scale, which is a critical step for practical applications. Graphene grain boundaries (GGBs), consisting of nonhexagonal carbon rings and therefore modulating the properties of graphene films, are inevitably formed via the merging of adjacent graphene domains with different orientations. Large-area monocrystalline graphene synthesis without forming GGBs has been challenging, let alone observing such boundaries. Here, an up-to-date review is presented of how to grow wafer-scale monocrystalline graphene without GGBs. One approach is to make single domain sizes as large as possible by reducing or passivating the number of nucleation sites. Another approach is to align graphene domains in identical orientations, and then merge them atomically. The recently developed methods for observing graphene orientation and GGBs both at the atomic and macro-scales are also presented. Finally, perspectives for future research in graphene growth are discussed.

Clean, flat and orientation-identified graphene on a substrate is in high demand for graphene electronics. In this study, the hetero-epitaxial graphene growth on Cu(111)/mica(001) by chemical vapor deposition is investigated to check the applicability for top-gate insulator research on graphene, as well as graphene channel research, by transferring graphene on to SiO2/Si substrates. After adjusting the graphene growth conditions, the surface roughness of the graphene/Cu/mica substrate and the average smoothed areas are ∼0.34 nm and ∼100 μm2, respectively. The orientation of graphene in the graphene/Cu/mica substrate can be identified by the hexagonal void morphology of Cu. Moreover, we demonstrate a relatively high mobility of ∼4500 cm2 V−1 s−1 in graphene transferred on the SiO2/Si substrate. These results suggest that the present graphene/Cu/mica substrate can be used for top-gate insulator research on graphene.

We report new findings on the chemical vapor deposition (CVD) of monolayer graphene with negligible defects (≥95% negligible defect-peak over 200 μm × 200 μm areas) on evaporated copper films. Compared to copper foils used in the CVD of graphene, several new unexpected results have been observed including high-quality monolayer synthesis at temperatures <900 °C, a new growth window using a hydrogen-free methane precursor for low-defects, and electron microscope evidence of commensurate growth of graphene grains on underlying copper grains. These thermal, chemical, and physical growth characteristics of graphene on copper films can be attributed to the distinct differences in the dominant crystal orientation of copper films (111) versus foils (100), and consequent dissimilar interplay with the precursor gas. This study suggests that reduced temperature, hydrogen-free synthesis of defect-negligible monolayer graphene is feasible, with the potential to shape and scale graphene grains by controlling the size and crystal orientation of the underlying copper grains.

Graphene, the two-dimensional network of sp²-hybridized carbon atoms, has attracted worldwide interest because of its unique energy band structure as well as its outstanding electronic, thermal and mechanical properties. The extremely high carrier mobility in graphene provides a great potential for next-generation ultrafast graphene-based electronic devices. One of the bottle-neck challenges for graphene electronics is the controlled growth of high-quality graphene. Among the typical techniques reported for graphene production, chemical vapor deposition (CVD) has been paid particular attention for its reliability and facile access to highly-crystalline and large-area graphene. We are working on controlled CVD growth of graphene following a concept of <italic>process engineering</italic>. Our general strategy is to design and control the elementary steps of catalytic CVD process for achieving a precise control over layer thickness, stacking order, domain size, doping and energy band structure. In this paper, we will show a few typical examples to demonstrate such kinds of <italic>process engineering </italic>for the designed growth of graphene together with a brief discussion on the future directions, challenges and opportunities in this fascinating research area.

ConspectusGraphene, a one-atom-thick layer of carbon with a honeycomb lattice, has drawn great attention due to its outstanding properties and its various applications in electronic and photonic devices. Mechanical exfoliation has been used for preparing graphene flakes (from monolayer to multilayer with thick pieces also typically present), but with sizes limited typically to less than millimeters, its usefulness is limited. Chemical vapor deposition (CVD) has been shown to be the most effective technique for the scalable preparation of graphene films with high quality and uniformity. To date, CVD growth of graphene on the most commonly used substrates (Cu and Ni foils) has been demonstrated and intensively studied. However, a survey of the existing literature and earlier work using Cu or Ni substrates for CVD growth indicates that the bilayer and multilayer graphene over a large area, particularly single crystals, have not been obtained.In this Account, we review current progress and development in the CVD growth of graphene and highlight the important challenges that need to be addressed, for example, how to achieve large single crystal graphene films with a controlled number of layers. A single-layer graphene film grown on polycrystalline Cu foil was first reported by our group, and since then various techniques have been devoted to achieving the fast growth of large-area graphene films with high quality. Commercially available Cu/Ni foils, sputtered Cu/Ni thin films, and polycrystalline Cu/Ni foils have been used for the CVD synthesis of bilayer, trilayer, and multilayer graphene. Cu/Ni alloy substrates are particularly interesting due to their greater carbon solubility than pure Cu substrates and this solubility can be finely controlled by changing the alloy composition. These substrates with controlled compositions have shown the potential for the growth of layer-tunable graphene films in addition to providing a much higher growth rate due to their stronger catalytic activity. However, the well-controlled preparation of single crystal graphene with a defined number of layers on Cu/Ni substrates is still challenging.Due to its small lattice mismatch with graphene, a single crystal Cu(111) foil has been shown to be an ideal substrate for the epitaxial growth of graphene. Our group has reported the synthesis of large-size single crystal Cu(111) foils by the contact-free annealing of commercial Cu foils, and single crystal Cu/Ni(111) alloy foils have also been obtained after the heat-treatment of Ni-coated Cu(111) foils. The use of these single crystal foils (especially the Cu/Ni alloy foils) as growth substrates has enabled the fast growth of single crystal single-layer graphene films. By increase of the Ni content, single crystal bilayer, trilayer, and even multilayer graphene films have been synthesized. In addition, we also discuss the wafer-scale growth of single-layer graphene on the single crystalline Cu/Ni(111) thin films.Recent research results on the large-scale preparation of single crystal graphene films with different numbers of layers on various types of Cu/Ni alloy substrates with different compositions are reviewed and discussed in detail. Despite the remarkable progress in this field, further challenges, such as the wafer-scale synthesis of single crystal graphene with a controlled number of layers and a deeper understanding of the growth mechanism of bilayer and multilayer graphene growth on Cu/Ni substrates, still need to be addressed.

Low energy electron diffraction study of high index copper surfaces underneath graphene

The use of solid-state carbon sources is effective to produce graphene by safe and low-cost chemical vapor deposition (CVD) process. Water-soluble polymers are generally environmentally friendly and have great potential on large-scale green production of graphene. Here, we systematically study the growth of graphene from water-soluble polymers on copper foils. Two different conversion ways are adopted to investigate the growth mechanism of graphene from water-soluble polymers. We find that the metal-binding functional group hydroxyl strongly influences the vaporization of water-soluble polymers on Cu foils, which hinders the formation of graphene films by rapid thermal treatment. In direct CVD process using water-soluble polymer powders as precursors, oxygenated functional groups in polymers can enhance the crystallinity of as-grown graphene in contrast to solid hydrocarbons without containing oxygen (e.g. polyethylene). Large and continuous graphene films of high quality are synthesized from polyvinyl alcohol and polyethylene glycol. Nitrogen doping in graphene can be easily realized by using nitrogen-containing water-soluble polymers (e.g. polyvinyl pyrrolidone).