Philipp Braeuninger-Weimer

CVD-Enabled Graphene Manufacture and Technology

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.

Controlling Catalyst Bulk Reservoir Effects for Monolayer Hexagonal Boron Nitride CVD.

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.

Understanding and Controlling Cu-Catalyzed Graphene Nucleation: The Role of Impurities, Roughness, and Oxygen Scavenging

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.

Graphene based plasmonic terahertz amplitude modulator operating above 100 MHz

The terahertz (THz) region of the electromagnetic spectrum holds great potential in many fields of study, from spectroscopy to biomedical imaging, remote gas sensing, and high speed communication. To fully exploit this potential, fast optoelectronic devices such as amplitude and phase modulators must be developed. In this work, we present a room temperature external THz amplitude modulator based on plasmonic bow-tie antenna arrays with graphene. By applying a modulating bias to a back gate electrode, the conductivity of graphene is changed, which modifies the reflection characteristics of the incoming THz radiation. The broadband response of the device was characterized by using THz time-domain spectroscopy, and the modulation characteristics such as the modulation depth and cut-off frequency were investigated with a 2.0 THz single frequency emission quantum cascade laser. An optical modulation cut-off frequency of 105 ± 15 MHz is reported. The results agree well with a lumped element circuit model developed to describe the device.

Measuring the proton selectivity of graphene membranes

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.

Extrinsic Cation Selectivity of 2D Membranes

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.

Parameter Space of Atomic Layer Deposition of Ultrathin Oxides on Graphene

Atomic layer deposition (ALD) of ultrathin aluminum oxide (AlOx) films was systematically studied on supported chemical vapor deposition (CVD) graphene. We show that by extending the precursor residence time, using either a multiple-pulse sequence or a soaking period, ultrathin continuous AlOx films can be achieved directly on graphene using standard H2O and trimethylaluminum (TMA) precursors even at a high deposition temperature of 200 °C, without the use of surfactants or other additional graphene surface modifications. To obtain conformal nucleation, a precursor residence time of >2s is needed, which is not prohibitively long but sufficient to account for the slow adsorption kinetics of the graphene surface. In contrast, a shorter residence time results in heterogeneous nucleation that is preferential to defect/selective sites on the graphene. These findings demonstrate that careful control of the ALD parameter space is imperative in governing the nucleation behavior of AlOx on CVD graphene. We consider our results to have model system character for rational two-dimensional (2D)/non-2D material process integration, relevant also to the interfacing and device integration of the many other emerging 2D materials.

Encapsulation of graphene transistors and vertical device integration by interface engineering with atomic layer deposited oxide

We demonstrate a simple, scalable approach to achieve encapsulated graphene transistors with negligible gate hysteresis, low doping levels and enhanced mobility compared to as-fabricated devices. We engineer the interface between graphene and atomic layer deposited (ALD) Al

External amplitude and frequency modulation of a terahertz quantum cascade laser using metamaterial/graphene devices

_{2}

Measuring the thermal properties of anisotropic materials using beam-offset frequency domain thermoreflectance

O