Understanding the Reaction Kinetics to Optimize Graphene Growth on Cu by Chemical Vapor Deposition

Abstract

Understanding and controlling the growth kinetics of graphene is a prerequisite to synthesize this highly wanted material by chemical vapor deposition on Cu, e.g. for the construction of ultra-stable electron transparent membranes. It is reviewed that Cu foils contain a considerable amount of carbon in the bulk which significantly exceeds the expected amount of thermally equilibrated dissolved carbon in Cu and that this carbon must be removed before any high quality graphene may be grown. Starting with such conditioned Cu foils, systematic studies of the graphene growth kinetics in a reactive CH 4 /H 2 atmosphere allow to extract the following meaningful data: prediction of the equilibrium constant of the graphene formation reaction within a precision of a factor of two, the confirmation that the graphene growth proceeds from a C(ad)-phase on Cu which is in thermal equilibrium with the reactive gas phase, its apparent activation barrier and finally the prediction of the achievable growth velocity of the growing graphene flakes during chemical vapor deposition. As a result of the performed study, growth parameters are identified for the synthesis of high quality monolayer graphene with single crystalline domains of 100-1000 μm in diameter within a reasonable growth time.

Quasistatic Equilibrium Chemical Vapor Deposition of Graphene

“…In addition, the various advantages of the CVD approach include those posed by the confinement concept as well. [ 11,13,14 ] Generally, a space‐restricted configuration poses two major advantages. First, the key objective of the space‐limited chamber is to reduce the carbon (C) flux and contain the growth substrate nearby for a longer period to increase the growth probability.…”

Controlled Island Formation of Large-Area Graphene Sheets by Atmospheric Chemical Vapor Deposition: Role of Natural Camphor

“…In this technique, the carbon precursors are decomposed on the Cu surfaces because of its low carbon solubility and the self-limiting factor. 6−10 The resulting graphene on the metal substrate can be easily transferred to any desirable substrates by a simple transferring process without affecting much of the properties of graphene. Recently, gaseous hydrocarbons and liquid carbon sources have been replaced by forthcoming solid carbon sources such as camphor (C 10 H 16 O), polystyrene, and so forth by a very facile and low cost approach to achieve a large-area MLG on Cu foil with an optimum optoelectronic properties.…”

“…15,16,19−22 There are various reports on the variation of annealing and gaseous flow rates to control the nucleation and growth kinetics of graphene crystals on substrate surfaces. 10,23−26 In addition, various temperature conditions give an indication on the control formation of monolayer, bilayer, hexagonal structure, layer-stacking, and dendrite growth of graphene. 27,28 In this regard, the key point for the present investigation is to achieve MLG on Cu foil with a large domain size that can deliver good optical and electrical properties.…”

Dissociation of CHD3 on Cu(111), Cu(211), and single atom alloys of Cu(111)

“…Moreover, methane dissociation on copper is a much investigated method for creating high quality graphene. [3][4][5][6][7][8][9] However, due to the complexity of the interaction between metals and molecules and of describing both metals and molecules accurately, this reaction remains difficult for theoretical studies. [10][11][12][13][14] Recently, it has been shown that chemically accurate results can be obtained for moleculesurface reactions by using a so-called Specific Reaction Parameter (SRP) approach.…”