Highly controlled Fe-catalyzed growth of monolayer hexagonal boron nitride (h-BN) films is demonstrated by the dissolution of nitrogen into the catalyst bulk via NH3 exposure prior to the actual growth step. This “pre-filling” of the catalyst bulk reservoir allows us to control and limit the uptake of B and N species during borazine exposure and thereby to control the incubation time and h-BN growth kinetics while also limiting the contribution of uncontrolled precipitation-driven h-BN growth during cooling. Using in situ X-ray diffraction and in situ X-ray photoelectron spectroscopy combined with systematic growth calibrations, we develop an understanding and framework for engineering the catalyst bulk reservoir to optimize the growth process, which is also relevant to other 2D materials and their heterostructures.

From a systematic study of the concentration driven diffusion of positive and negative ions across porous 2D membranes of graphene and hexagonal boron nitride (h-BN), we prove their cation selectivity. Using the current–voltage characteristics of graphene and h-BN monolayers separating reservoirs of different salt concentrations, we calculate the reversal potential as a measure of selectivity. We tune the Debye screening length by exchanging the salt concentrations and demonstrate that negative surface charge gives rise to cation selectivity. Surprisingly, h-BN and graphene membranes show similar characteristics, strongly suggesting a common origin of selectivity in aqueous solvents. For the first time, we demonstrate that the cation flux can be increased by using ozone to create additional pores in graphene while maintaining excellent selectivity. We discuss opportunities to exploit our scalable method to use 2D membranes for applications including osmotic power conversion.

‡) equal contributionWe report high room-temperature mobility in single layer graphene grown by Chemical Vapor Deposition (CVD) after wet transfer on SiO2 and hexagonal boron nitride (hBN) encapsulation. By removing contaminations trapped at the interfaces between single-crystal graphene and hBN, we achieve mobilities up to∼ 70000cm 2 V −1 s −1 at room temperature and∼ 120000cm 2 V −1 s −1 at 9K. These are over twice those of previous wet transferred graphene and comparable to samples prepared by dry transfer. We also investigate the combined approach of thermal annealing and encapsulation in polycrystalline graphene, achieving room temperature mobilities∼ 30000cm 2 V −1 s −1 . These results show that, with appropriate encapsulation and cleaning, room temperature mobilities well above 10000cm 2 V −1 s −1 can be obtained in samples grown by CVD and transferred using a conventional, easily scalable PMMA-based wet approach. * al515@cam.ac.uk[1] S. M. Sze and K. K. Ng, Physics of semiconductor devices, (John Wiley & Sons, 2006).

The mechanism by which Cu catalyst pretreatments control graphene nucleation density in scalable chemical vapor deposition (CVD) is systematically explored. The intrinsic and extrinsic carbon contamination in the Cu foil is identified by time-of-flight secondary ion mass spectrometry as a major factor influencing graphene nucleation and growth. By selectively oxidizing the backside of the Cu foil prior to graphene growth, a drastic reduction of the graphene nucleation density by 6 orders of magnitude can be obtained. This approach decouples surface roughness effects and at the same time allows us to trace the scavenging effect of oxygen on deleterious carbon impurities as it permeates through the Cu bulk. Parallels to well-known processes in Cu metallurgy are discussed. We also put into context the relative effectiveness and underlying mechanisms of the most widely used Cu pretreatments, including wet etching and electropolishing, allowing a rationalization of current literature and determination of the relevant parameter space for graphene growth. Taking into account the wider CVD growth parameter space, guidelines are discussed for high-throughput manufacturing of “electronic-quality” monolayer graphene films with domain size exceeding 1 mm, suitable for emerging industrial applications, such as electronics and photonics.

Integrated manufacturing is arguably the most challenging task in the development of technology based on graphene and other 2D materials, particularly with regard to the industrial demand for “electronic-grade” large-area films. In order to control the structure and properties of these materials at the monolayer level, their nucleation, growth and interfacing needs to be understood to a level of unprecedented detail compared to existing thin film or bulk materials. Chemical vapor deposition (CVD) has emerged as the most versatile and promising technique to develop graphene and 2D material films into industrial device materials and this Perspective outlines recent progress, trends, and emerging CVD processing pathways. A key focus is the emerging understanding of the underlying growth mechanisms, in particular on the role of the required catalytic growth substrate, which brings together the latest progress in the fields of heterogeneous catalysis and classic crystal/thin-film growth.

By systematically studying the proton selectivity of free-standing graphene membranes in aqueous solutions we demonstrate that protons are transported by passing through defects. We study the current-voltage characteristics of single-layer graphene grown by chemical vapour deposition (CVD) when a concentration gradient of HCl exists across it. Our measurements can unambiguously determine that H + ions are responsible for the selective part of the ionic current. By comparing the observed reversal potentials with positive and negative controls we demonstrate that the as-grown graphene is only weakly selective for protons. We use atomic layer deposition to block most of the defects in our CVD graphene. Our results show that a reduction in defect size decreases the ionic current but increases proton selectivity.

A first-order model for graphene CVD on transition metal catalysts that combines kinetic and thermodynamic considerations is developed and experimentally verified.

Hexagonal boron nitride (h-BN) is the only known material aside from graphite with a structure composed of simple, stable, non-corrugated atomically thin layers. While historically used as lubricant in powder form, h-BN layers have become particularly attractive as an ultimately thin insulator. Practically all emerging electronic and photonic device concepts rely on h-BN exfoliated from small bulk crystallites, which limits device dimensions and process scalability.Here, we address this integration challenge for mono-layer h-BN via a chemical vapour deposition process that enables crystal sizes exceeding 0.5 mm starting from commercial, reusable platinum foils, and in unison allows a delamination process for easy and clean layer transfer. We demonstrate sequential pick-up for the assembly of graphene/h-BN heterostructures with atomic layer precision, while minimizing interfacial contamination. Our process development builds on a systematic understanding of the underlying mechanisms. The approach can be readily combined with other layered materials and opens a scalable route to h-BN layer integration and reliable 2D material device layer stacks.