The preparation of two-dimensional transition metal dichalcogenides on an industrially relevant scale will rely heavily on bottom-up methods such as chemical vapour deposition. In order to obtain sufficiently large quantities of high-quality material, a knowledge-based optimization strategy for the synthesis process must be developed. A major problem that has not yet been considered is the degradation of materials by etching during synthesis due to the high growth temperatures. To address this problem, we introduce a mathematical model that accounts for both growth and, for the first time, etching to describe the synthesis of two-dimensional transition metal dichalcogenides. We consider several experimental observations that lead to a differential equation based on several terms corresponding to different supply mechanisms, describing the time-dependent change in flake size. By solving this equation and fitting two independently obtained experimental data sets, we find that the flake area is the leading term in our model. We show that the differential equation can be solved analytically when only this term is considered, and that this solution provides a general description of complex growth and shrinkage phenomena. Physically, the dominance suggests that the supply of material via the flake itself contributes most to its net growth. This finding also implies a predominant interplay between insertion and release of atoms and their motion in the form of a highly dynamic process within the flake. In contrast to previous assumptions, we show that the flake edges do not play an important role in the actual size change of the two-dimensional transition metal dichalcogenide flakes during chemical vapour deposition.
The outstanding electrical and mechanical properties of graphene make it very attractive for several applications, Nanoelectronics above all. However a reproducible and non destructive way to produce high quality, large-scale area, single layer graphene sheets is still lacking. Chemical Vapour Deposition of graphene on Cu catalytic thin films represents a promising method to reach this goal, because of the low temperatures (T < 900 Celsius degrees) involved during the process and of the theoretically expected monolayer self-limiting growth. On the contrary such self-limiting growth is not comm…
Understanding the mechanisms involved in chemical vapour deposition (CVD) synthesis of atomically thin transition metal dichalcogenides (TMDCs) requires the precise control of numerous growth parameters. All the proposed mechanisms and their relation to the growth conditions are inferred from characterising intermediate formations obtained by stopping the growth blindly. To fully understand the reaction routes that lead to the monolayer formation, real time observation and control of the growth are needed. Here, we demonstrate how a custom-made CVD chamber that allows real time optical monitor…
Alloying/doping in two-dimensional material has been important due to wide range band gap tunability. Increasing the number of components would increase the degree of freedom which can provide more flexibility in tuning the band gap and also reduced the growth temperature. Here, we report synthesis of quaternary alloys MoxW1-xS2ySe2(1-y) using chemical vapour deposition. The composition of alloys has been tuned by changing the growth temperatures. As a result, we can tune the bandgap which varies from 1.73 eV to 1.84 eV. The detailed theoretical calculation supports the experimental observatio…
In order to improve the performance of existing technologies based on single crystal diamond grown by chemical vapour deposition (CVD), and to open up new technologies in fields such as quantum computing or solid state and semiconductor disc lasers, control over surface and bulk crystalline quality is of great importance. Inductively coupled plasma (ICP) etching using an Ar/Cl gas mixture is demonstrated to remove sub-surface damage of mechanically processed surfaces, whilst maintaining macroscopic planarity and low roughness on a microscopic scale. Dislocations in high quality single crystal …
Most III-nitride semiconductors are grown on non-lattice-matched substrates like sapphire or silicon due to the extreme difficulty of obtaining a native GaN substrate. We show that several layered transition-metal dichalcogenides are closely lattice matched to GaN and report the growth of GaN on a range of such layered materials. We report detailed studies of the growth of GaN on mechanically-exfoliated flakes WS$_2$ and MoS$_2$ by metalorganic vapour phase epitaxy. Structural and optical characterization show that strain-free, single-crystal islands of GaN are obtained on the underlying chalc…
Focused ion beams (FIBs) are widely used to modify optoelectronic devices, but their utility is severely restricted in some III-V materials due to adverse effects such as nanofibre growth and contamination. This study describes an effective machining method for the modification and passivation of GaSb using a focused Ga$^+$ beam with the addition of XeF$_2$ gas. The added gas suppressed the nanofibre growth and allowed for controlled etching. Moreover, the milled surface exhibited much lower roughness and contained much lower levels of carbon and oxygen contaminants. These effects are attribut…
CVD growth is capable of producing multiple single crystal islands of atomically thin TMDs over large area substrates, with potential control of their morphology, lateral size, and epitaxial alignment to substrates with hexagonal symmetry. Subsequent merging of epitaxial domains can lead to single-crystal monolayer sheets - a step towards scalable production of high quality TMDs. For CVD growth to be effectively used for such production it is necessary to be able to rapidly assess the quality of material across entire large area substrates. To date characterisation has been limited to sub 0.1 …
Layered inorganic materials, such as the transition metal dichalcogenides (TMDs), have attracted much attention due to their exceptional electronic and optical properties. Reliable synthesis and characterization of these materials must be developed if these properties are to be exploited. Herein, we present low-frequency Raman analysis of MoS2, MoSe2, WSe2 and WS2 grown by chemical vapour deposition (CVD). Raman spectra are acquired over large areas allowing changes in the position and intensity of the shear and layer-breathing modes to be visualized in maps. This allows detailed characterizat…
The present work deals with the synthesis of crystalline carbon nitride thin films by microwave plasma assisted chemical vapour deposition in N$_2$/CH$_4$ gas mixture. The discharge analysis by optical emission spectroscopy shows that the increase in the N$_2$/CH$_4$ ratio involves an important production of the CN and C$_2$ radicals. In the films X-ray energy dispersion spectroscopy shows that the N/C ratio decreases when the CH$_4$ percentage in N$_2$ increases. Xray diffraction and electron diffraction are used to study the carbon nitride films nature. Scanning electron microscopy shows tha…
Modulating electronic structure of monolayer transition metal dichalcogenides (TMDCs) is important for many applications and doping is an effective way towards this goal, yet is challenging to control. Here we report the in-situ substitutional doping of niobium (Nb) into TMDCs with tunable concentrations during chemical vapour deposition. Taking monolayer WS2 as an example, doping Nb into its lattice leads to bandgap changes in the range 1.98 eV to 1.65 eV. Noteworthy, electrical transport measurements and density functional theory calculations show that the 4d electron orbitals of the Nb dopa…
Transition metal dichalcogenides (TMDs) represent a large family of high-quality 2D materials with attractive electronic, thermal, chemical, and mechanical properties. Chemical vapour deposition (CVD) technique is currently the most reliable route to synthesis few-atomic layer thick and large-scale TMDs films. However, the effects of grain boundaries formed during the CVD method on the properties of TMDs nanomembranes have remained less explored. In this study, we therefore aim to investigate the thermal conduction along polycrystalline molybdenum disulfide (MoS2) as the representative member …
The ability to extract materials just a few atoms thick has led to discovery of graphene, monolayer transition metal dichalcogenides (TMDs), and other important two-dimensional materials. The next step in promoting understanding and utility of the flatland physics beyond the state-of-the-art is to study one-dimensional edges of such two-dimensional materials as well as to control the edge-plane ratio. Edges typically exhibit properties that are unique and distinctly different from those of planes and bulk. Thus, controlling them allows to design principally new materials with synthetic edge-pl…
Nanostructuring allows altering of the electronic and photonic properties of two-dimensional (2D) materials. The efficiency, flexibility, and convenience of top-down lithography processes are however compromised by nm-scale edge roughness and resolution variability issues, which especially affects the performance of 2D materials. Here we study how dry anisotropic etching of multilayer 2D materials with sulfur hexafluoride (SF6) may overcome some of these issues, showing results for hexagonal boron nitride (hBN), tungsten disulfide (WS2), tungsten diselenide (WSe2), molybdenum disulfide (MoS2),…
Low carrier mobility and high electrical contact resistance are two major obstacles prohibiting explorations of quantum transport in TMDCs. Here, we demonstrate an effective method to establish low-temperature Ohmic contacts in boron nitride encapsulated TMDC devices based on selective etching and conventional electron-beam evaporation of metal electrodes. This method works for most extensively studied TMDCs in recent years, including MoS2, MoSe2, WSe2, WS2, and 2H-MoTe2. Low electrical contact resistance is achieved at 2 K. All of the few-layer TMDC devices studied show excellent performance …
Innovative applications based on two-dimensional solids require cost-effective fabrication processes resulting in large areas of high quality materials. Chemical vapour deposition is among the most promising methods to fulfill these requirements. However, for 2D materials prepared in this way it is generally assumed that they are of inferior quality in comparison to the exfoliated 2D materials commonly used in basic research. In this work we challenge this assumption and aim to quantify the differences in quality for the prototypical transition metal dichalcogenide MoS$_2$. To this end single …
Hexagonal boron nitride (h-BN) is well-established as a requisite support, encapsulant and barrier for 2D material technologies, but also recently as an active material for applications ranging from hyperbolic metasurfaces to room temperature single-photon sources. Cost-effective, scalable and high quality growth techniques for h-BN layers are critically required. We utilise widely-available iron foils for the catalytic chemical vapour deposition (CVD) of h BN and report on the significant role of bulk dissolved species in h-BN CVD, and specifically, the balance between dissolved oxygen and ca…
Monolayer transition metal dichalcogenides (TMDCs) are two-dimensional (2D) materials with many potential applications. Chemical vapour deposition (CVD) is a promising method to synthesize these materials. However, CVD-grown materials generally have poorer quality than mechanically exfoliated ones and contain more defects due to the difficulties in controlling precursors' distribution and concentration during growth where solid precursors are used. Here, we propose to use thiol as a liquid precursor for CVD growth of high quality and uniform 2D MoS2. Atomic-resolved structure characterizations…
Two-dimensional (2D) materials offer opportunities to explore both fundamental science and applications in the limit of atomic thickness. Beyond the prototypical case of graphene, other 2D materials have recently come to the fore. Of particular technological interest are 2D semiconductors, of which the family of materials known as the group-VI transition metal dichalcogenides (TMDs) has attracted much attention. The presence of a bandgap allows for the fabrication of high on-off ratio transistors and optoelectronic devices, as well as valley/spin polarized transport. The technique of chemical …
Two-dimensional transition metal dichalcogenides (TMDCs) have properties attractive for optoelectronic and quantum applications. A crucial element for devices is the metal-semiconductor interface. However, high contact resistances have hindered progress. Quantum transport studies are scant as low-quality contacts are intractable at cryogenic temperatures. Here, temperature-dependent transfer length measurements are performed on chemical vapour deposition grown single-layer and bilayer WS$_2$ devices with indium alloy contacts. The devices exhibit low contact resistances and Schottky barrier he…
Defects play a significant role in optical properties of semiconducting two-dimensional transition metal dichalcogenides (TMDCs). In ultra-thin MoSe2, a remarkable feature at ~250 cm-1 in Raman spectra is ascribed to be a defect-related mode. Recent attempts failed to explain the origin of this peak, leaving it being a mystery. Here in this work, we demonstrate that this peak is a Se vacancy induced defect mode. Heat effect and hydrogen etching are two main factors to introduce Se vacancies in CVD process of growing MoSe2. A phonon confinement model can well explain the behaviors of intrinsic …
Alloying enables engineering of the electronic structure of semiconductors for optoelectronic applications. Due to their similar lattice parameters, the two-dimensional semiconducting transition metal dichalcogenides of the MoWSeS group (MX2 where M= Mo or W and X=S or Se) can be grown as high-quality materials with low defect concentrations. Here we investigate the atomic and electronic structure of Mo(1-x)WxS2 alloys using a combination of high-resolution experimental techniques and simulations. Analysis of the Mo and W atomic positions in these alloys, grown by chemical vapour transport, sh…
The integration of two-dimensional transition metal dichalcogenide crystals (TMDCs) into a dielectric environment is critical for optoelectronic and photonic device applications. Here, we investigate the effects of direct deposition of different dielectric materials (Al$_2$O$_3$, SiO$_2$, SiN$_x$) onto atomically thin (monolayer) TMDC WS$_2$ on its optical response. Atomic layer deposition (ALD), electron beam evaporation (EBE), plasma enhanced chemical vapour deposition (PECVD), and magnetron sputtering methods of material deposition are investigated. The photoluminescence (PL) measurements r…
