Tribology of Graphene: Simulation Methods, Preparation Methods, and Their Applications

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Chapter 1

Introduction to graphene

Abstract

This chapter is a brief introduction to graphene and its structure. First, it introduces critical nomenclature. Then, the structures of graphene and its derivatives such as graphene oxide are described. The second part is dedicated to necessary information about various structural defects of graphene, which are vital for mechanical and tribological properties. Finally, experimentally obtained mechanical properties of graphene are discussed.

Keywords

Graphene; Graphene oxide; Reduced graphene oxide; Structural defects; Mechanical properties

Contents

1.1Introduction to graphene structure

1.2Defects in graphene

1.3Derivatives of graphene

1.4Mechanical properties of graphene

References

1.1 Introduction to graphene structure

Carbon is one of the most essential materials for organic life, and graphene is the name of one of the carbon allotropes. The word graphene consists of the prefix graph, which comes from graphite, and the suffix ene, which represents the carbon/carbon double bonds [1]. In general, the word graphene refers to a monolayer of sp²-hybridized carbon atoms packed into a two-dimensional (2D) honeycomb structure that is partially filled with π-orbitals above and below the monolayer [2]. The graphene monolayer is atomically flat with the Van der Waals thickness of ~ 0.34 nm. This monolayer represents a building block for all other graphitic materials. Graphene can exist not only in the form of the single monolayer (sheet) but also in the multilayer form where several sheets are stacked together, forming a three-dimensional (3D) structure (Fig. 1.1). Beside the forming of 3D graphite, graphene can be wrapped up into zero-dimensional (0D) fullerenes or rolled into one-dimensional (1D) nanotubes (Fig. 1.2) [3].

Fig. 1.1 Formation of 3D graphene from a 2D building block—three common graphite structures with different graphene stacking arrangements: hexagonal stacking (AA), Bernal stacking (AB), and rhombohedral stacking (ABC).

Fig. 1.2 A 2D graphene sheet is the base for other allotropes: 0D (fullerene) and 1D (carbon nanotube).

Initially, it was assumed that graphene could not be standalone because of the predicted thermodynamic instability of 2D crystals [2]. Nonetheless, the theoretical predictions about this material became real in 2004 when it was demonstrated that isolated 2D structures can not only be stable at room temperature and in the air, but also maintain macroscopic continuity [4].

Graphene is a fundamental element of a large group of 2D and 3D carbon forms that includes materials with very different properties, lateral sizes, and number of layers. The term graphene can be prefixed by bilayer, few-layer, or multilayer. This classification is essential because the properties of mono-, bi- and multilayer graphene differ from the properties of graphite and each other [1, 2]. Besides, different names can be used for the same structures. For example, multilayer nanosheet has the same meaning as few-layer nanoplate. The most commonly used terminology of graphene is summarized in Table 1.1.

Table 1.1

There are three possible stacking configurations of few-layer graphene (Fig. 1.1): Bernal (AB), hexagonal (AA), and rhombohedral (ABC) [5, 6]. These stacking configurations differ in the relative orientation of the graphene layer stacks that may be crucial for some applications. For instance, the stacking order significantly affected the electronic structure of few-layer graphene [5]. Among the possible stacking configurations, the Bernal configuration has the lowest stacking energy [7]. This configuration is formed by stacking two graphene sheets rotated by 60 degrees relative to each other around the z-axis. In this case, the 3D unit cell has four atoms, and a third basis vector perpendicular to the graphene layer stacks is 0.6672 and 0.6708 nm at 4.2 and 297 K, respectively [8].

In the case of AA-stacked graphene, all carbon atoms in every sheet have the same x and y coordinates (Fig. 1.1). In the ABC structure, half the atoms are located directly below atoms in the adjacent layer and directly above the hexagonal ring centers while the other half of the atoms are directly above atoms and directly below hexagonal ring centers [9]. Even though the Bernal stacking is the most common configuration in single-crystal graphite, it was found that 15% of the exfoliated multilayer graphene is composed of micrometer-sized domains of rhombohedral stacking, rather than the usual Bernal stacking [10]. Stacking order may be crucial for the mechanical behavior of several-layer graphene, especially on the macroscopic level. For instance, different lengths of the upper and lower layers of graphene in the case of AB stacking led to a stress concentration at the boundary of the short layers of graphene [11].

Many properties of graphene are affected by chirality or orientation. Because graphene has a hexagonal lattice, there are two types of edges, called zigzag and armchair (Fig. 1.3). Zigzag and armchair edges also could be drawn as lateral and longitudinal edges [12]. In the case of nanoribbons, zigzag graphene and armchair graphene definitions can be used. Here, the name is defined by the edge type along the longest dimension of a nanoribbon.

Fig. 1.3 Two types of edges in graphene: (A) zigzag and (B) armchair. The edges are indicated by bold lines.

1.2 Defects in graphene

Various types of structural defects may appear during the synthesis of graphene. Because sp²-hybridized carbon atoms can rearrange themselves into various polygons and form different structures, the formation of nonhexagonal rings may occur [13]. Such nonhexagonal structures could be considered as structural defects of the ideal hexagonal lattice. Depending on their configuration, nonhexagonal rings could produce curvature of the graphene sheet or leave it flat if the arrangement of polygons satisfies certain symmetry rules. Such behavior is attributed only to 2D structures and could not be found in bulk crystals [13].

Several experimental studies reported the existence of either native or physically introduced structural defects in graphene. The presence of defects is essential for the mechanical and tribological properties of graphene materials. Defects in graphene structure are referred to as intrinsic or extrinsic, depending on their nature. Intrinsic defects resulted in the form of perturbation of the original crystal structure without the presence of foreign atoms. Foreign atoms are denoted as impurities and constitute extrinsic defects [14]. Due to the reduced dimensionality of graphene, the number of possible defects is reduced in comparison to 3D materials. The 0D point defects in graphene are similar to one of the bulk crystals, line defects are different, and 3D defects do not exist. Graphene defects have certain mobility in the graphene plane. The migration mobility of various types of defects is governed by their activation energy and exponentially increases with temperature [14].

Several point defects of graphene such as mono- and di-vacancies, adatoms, and Stone-Wales (SW) defects are known. Defects in graphene are illustrated in Fig. 1.4. The monovacancy is the missing lattice atom; this is the simplest point defect in a graphene structure (Fig. 1.4A). The formation of the monovacancy led to the creation of nine- and five-membered rings, also called the 5-9 cluster. The formation energy of the monovacancy is about 7.5 eV [15]. Due to having a dangling bond, the monovacancy is highly reactive and can be quickly demolished.

Fig. 1.4 Schematics of point defects in graphene. (A) mono-vacancy; (B) di-vacancy; and (C) Stone-Wale defect (SW); the boundary of defects is indicated by bold lines.

Divacancy (DV) in graphene has no dangling bond (Fig. 1.4B). Due to the lower energy of formation, it is much more stable and less reactive [16]. It could be formed by the coalescence of two monovacancies or by the removing of two neighboring atoms. Thus, two pentagons and one octagon are built instead of four hexagons, forming a 5-8-5 cluster [14]. The formation energy of the divacancy is very close to one of the monovacancies [15]. But because of two missing atoms, the energy per atom would be significantly lower, making the formation of DV thermodynamically preferable [13]. Beside the 5-8-5 configuration, there are several other ways for a graphene lattice to accommodate two missing atoms. Moreover, this configuration is not energetically preferred. Other arrangements such as 555-777 or 5555-6-7777 have lower formation energy [14].

The elimination of more than two atoms may cause the formation of a larger and more complex configuration of defects. Because an even number of missing atoms allows the full recombination of dangling bonds, such defects are energetically preferable over defects having an odd number of missing atoms due to the remaining of the open bond [14]. The formation of large holes with unsaturated bonds is more likely in the case of simulations removing a large number of atoms.

One of the exceptional properties of graphene lattice is the ability to reorder by establishing nonhexagonal rings without missing atoms [14]. The simplest example of such rearrangement is the formation of the SW defect (Fig. 1.4C). It forms due to a change of connectivity of two π-bonded carbon atoms, which led to a 90 degree in-plane rotation of the bond [17]. Four hexagons are transformed into two pentagons and two heptagons, forming a so-called 5-7-7-5 cluster. Thus, the formation of the SW defect does not involve any removed or added atom, and no dangling bonds are introduced [14]. The formation energy of the 5-7-7-5 defect is about 5 eV [18].

The formation of interstitial atoms as occurred in bulk crystals is not possible in graphene because adding an atom to any in-plane position such as the center of a hexagon would require excessively high energy. Thus, in graphene, adatoms are located in the third dimension. The energetically preferred position would be the top of a carbon-carbon bond (the bridge configuration). The formation of such a structure led to the changing of hybridization. Due to the appearance of some sp³ hybridization, the formation of two covalent bonds between the adatom and the underlying atoms in the graphene plane takes place [14].

One-dimensional defects such as dislocations and grain boundaries were observed in several experimental studies of graphene. Generally, these defects are tilt boundaries separating two domains with different lattice orientations. Such defects could be imagined as a line of point defects with or without dangling bonds [14]. The formation of line defects can occur in the case of simultaneous nucleation of graphene layers in different locations followed by their coalescence. This process is similar to the creation of grain boundaries in bulk crystals.

The presence of atomic-scale steps is a ubiquitous feature of multilayer graphene. There are two types of step edges (Fig. 1.5). The first type is internal or covered steps, which formed during the graphene growth (Section 3.3). The second type is external (uncovered) steps usually created during the mechanical cleavage of HOPG (Section 3.1). The presence of dangling bonds on the exposed edges makes them chemically active. A higher work function was observed on the external steps compared with other internal steps due to step dipoles and adsorbates [19].

Fig. 1.5 Covered and uncovered step edges of graphene.

1.3 Derivatives of graphene

Significant attention was first paid to pristine graphene because of its unique electronic properties. This made graphene a model system for the observation of a novel quantum phenomenon and the building block for future nanoelectronic devices [3]. Nevertheless, from a practical point of view, industrial applications are required to produce graphene in significantly large quantiles. One of the approaches to increase the production rate of graphene is fabrication by the reduction of graphene oxide (GO) because it demonstrated the potential of cost-effective, large-scale production of graphene-based materials [20]. Since it was first synthesized in the nineteenth century, GO has been a popular graphene derivative. GO is a single-carbon monolayer with randomly distributed aromatic regions (sp² carbon atoms) and oxygenated aliphatic domains (sp³ carbon atoms) containing carbonyl, carboxyl, epoxy, and hydroxyl functional groups (Fig. 1.6). The presence of the functional groups makes GO hydrophilic [21].

Fig. 1.6 Comparison of the chemical structures of graphene, GO, and rGO.

GO is synthesized by the oxidation of graphite in the presence of a strong acid and an oxidizing agent. The oxidation process leads to a partial disruption in the sp² hybridized structure of graphite and to an increase of the distance between its carbon layers, leading to final separation to sheets that are a single carbon atom thick [21]. Graphene oxide sheets are thicker than graphene due to the displacement of sp³ hybridized carbon atoms slightly above and below the original graphene plane and the presence of covalently bound oxygen atoms [3]. The level of the oxidation can be varied depending on the method, the reaction conditions, and the graphite precursor. Although extensive research has been done to reveal the chemical structure of GO, several models of this process are still being debated in the literature [20].

Reduced graphene oxide (rGO) is also a 2D single-atom-thick material. It is like graphene, but it has extra carbon ring domains, defects, and remaining oxygen-containing groups (-OH, -COOH, etc.) on the surface (Fig. 1.6). The initial goal of reducing GO was to fabricate graphene materials comparable to the structure and properties of pure graphene achieved by mechanical exfoliation.

1.4 Mechanical properties of graphene

The mechanical properties of graphene are the main reason that it is a primary tribological material of the future. It has the highest strength and elastic modulus after carbon nanotubes. The exceptional mechanical properties of graphene are based on the stability of sp² bonds forming the hexagonal lattice. That allows a graphene sheet to oppose in-plane deformations [22]. For the first time, the mechanical properties of free-standing monolayer graphene were measured by Lee et al. using the nanoindentation mode of AFM [23]. It was demonstrated that the monolayer graphene membrane had a Young's modulus of ~1 TPa. Hoverer, different stiffness values were obtained in some reports. This difference was attributed to the unrecordable crumpling of graphene sheets that may originate from point defects or uneven stress at the boundaries [22]. The transfer process used after the CVD process almost always causes wrinkling and damage, which also may reduce the mechanical properties. The shear modulus of CVD-grown monolayer graphene (Section 3.3) was measured by Lui et al. [24]. A value of 280 GPa was