Graphene growth process modeling: a physical–statistical approach

Inductively coupled remote plasma-enhanced chemical vapor deposition (rPE-CVD) as a versatile route for the deposition of graphene micro- and nanostructures

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.

Demonstration of enhanced the photocatalytic effect with PtSe2 and TiO2 treated large area graphene obtained by CVD method

Graphene growth by low-pressure chemical vapor deposition on low cost copper foils shows great promise for large scale applications. It is known that the local crystallography of the foil influences the graphene growth rate. Here we find an epitaxial relationship between graphene and copper foil. Interfacial restructuring between graphene and copper drives the formation of (n10) facets on what is otherwise a mostly Cu(100) surface, and the facets in turn influence the graphene orientations from the onset of growth. Angle resolved photoemission shows that the electronic structure of the graphene is decoupled from the copper indicating a weak interaction between them. Despite this, two preferred orientations of graphene are found, ±8° from the Cu[010] direction, creating a non-uniform distribution of graphene grain boundary misorientation angles. Comparison with the model system of graphene growth on single crystal Cu(110) indicates that this orientational alignment is due to mismatch epitaxy. Despite the differences in symmetry the orientation of the graphene is defined by that of the copper. We expect these observations to not only have importance for controlling and understanding the growth process for graphene on copper, but also to have wider implications for the growth of two-dimensional materials on low cost metal substrates.

Self-limited growth of large-area monolayer graphene films by low pressure chemical vapor deposition for graphene-based field effect transistors

The controlled growth of large-area single-crystalline graphene via epitaxial methods such as chemical vapor deposition (CVD) is essential in the eventual widespread realization of graphene-based devices. In this endeavor, one startling obstacle is the emergence of abundant grain boundaries in a growing graphene layer. Here, we carry out comparative studies of single-layer graphene films grown on optimized Cu(111) and Cu–Ni(111) alloyed substrates using various experimental probes and first-principles calculations. We demonstrate, convincingly, that the use of the Ni substitutionally alloyed Cu substrate results in drastic elimination of grain boundaries in graphene films compared to those grown on pure Cu. The underlying mechanism of the highly preferred single-crystalline growth is the elimination of the orientational disorder of multiple initial nucleation islands on the Cu–Ni(111) surface, as demonstrated theoretically and confirmed experimentally. The present study not only unveils the atomistic growth mechanism of single-crystalline monolayered graphene on Cu–Ni alloys with a fast growth rate and mass productivity but also sheds light on the controlled CVD growth of large-area twist-angle bilayer graphene, multilayered graphene, and other 2D vdW materials in general.

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.

Promoter-assisted chemical vapor deposition of graphene

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.

Attractive attributes of carbon nanotubes (CNTs),, which include high aspect ratio, excellent electrical and thermal conductivity, high melting point, and longer lifetime, have made this one-dimensional material a promising candidate for next-generation field emitters. In the present work, CNTs were grown directly on copper foil, copper foam, nickel foil and nickel foam through chemical vapor deposition. A comparison between CNT-based two-dimensional emitters, i.e. CNTs synthesized on copper and nickel foils, CNT-based three-dimensional (3D) emitters, i.e. CNTs developed on foams of copper and nickel, have been demonstrated. We observed that CNTs on foams exhibited better field emission compared to CNTs synthesized on foils. This is due to the multistage structure of the 3D foams which provides high surface area for CNT growth and hence enhanced field emission response. In the present work, a CNT sample prepared on nickel foam was observed to exhibit better field emission response compared to the other samples synthesized in the present study. This particular sample demonstrateda very low turn-on field of 0.93 V/µm, excellent field enhancement factor of 13,343 and good stability of electron emission.

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.

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

The evolution of SiC surface morphology during graphene growth process has been studied through the comparison of substrate surface step structure after in-situ etching and graphene growth in vacuum. Influence of in-situ substrate surface preparation on the properties of graphene was studied through the comparison of graphene layers on etched and un-etched substrates grown under same conditions.

Freestanding graphene films are desired to be widely applied in biosensor fabrication due to their distinctive physical properties and improved performance. Chemical vapor deposition has been developed to efficiently fabricate large-area graphene. However, some of the fabricated graphene films might break or be contaminated in the current transferring step using polymers. A stable and high-quality transfer method is needed. Herein, we report on an advanced transfer method of large-area graphene film which uses fullerene as a supporting substrate. Unlike polymers, which are commonly eliminated by being dissolved in an organic solution, fullerene can be easily removed by evaporation in a vacuum because it has a different heat stability to graphene. By using the improved transferring method, the percentage of integrated freestanding films after transferring was increased from 60.7% to 93.4%. The vacuum is beneficial in terms of keeping the brittle freestanding films intact. Graphene films transferred using fullerene showed an advanced flatness and a simplicial elementary composition in comparison to those transferred using polymers. Even through there is trace residue, this stable allotrope of graphene is considered to have almost no impact on biomolecule sensing. These advantages make the fullerene transferring method an attractive candidate for fabricating large-area freestanding graphene films, especially for using in the field of biochemistry analysis and biosensors.