High-efficiency dual single layer graphene modulator integrated on slot waveguides.

This paper presents an experimental and theoretical investigation of a graphene-integrated electro-absorption modulator (EAM) based on a slot waveguide. Due to the enhanced light-matter interaction of graphene, the device exhibits an impressive modulation efficiency (0.038 dBµm-1V-1) and bandwidth (≈ 16 GHz). Starting from these results, we carried out an extensive design study, focusing on three crucial design parameters and exploring the associated trade-offs in insertion loss, extinction ratio and bandwidth. The simulation results offer valuable insights into the influence of each design parameter, reaffirming that our slot waveguide platform holds great promise for realizing a high-performance EAM balancing optical and electrical performance. It is important to note that the slot waveguide was defined through standard deep ultraviolet (DUV) lithography, allowing seamless integration into high-density systems.

Enhanced Thermal Conductivity of Free-Standing Double-Walled Carbon Nanotube Networks.

Nanomaterials are driving advances in technology due to their oftentimes superior properties over bulk materials. In particular, their thermal properties become increasingly important as efficient heat dissipation is required to realize high-performance electronic devices, reduce energy consumption, and prevent thermal damage. One application where nanomaterials can play a crucial role is extreme ultraviolet (EUV) lithography, where pellicles that protect the photomask from particle contamination have to be transparent to EUV light, mechanically strong, and thermally conductive in order to withstand the heat associated with high-power EUV radiation. Free-standing carbon nanotube (CNT) films have emerged as candidates due to their high EUV transparency and ability to withstand heat. However, the thermal transport properties of these films are not well understood beyond bulk emissivity measurements. Here, we measure the thermal conductivity of free-standing CNT films using all-optical Raman thermometry at temperatures between 300 and 700 K. We find thermal conductivities up to 50 W m-1 K-1 for films composed of double-walled CNTs, which rises to 257 W m-1 K-1 when considering the CNT network alone. These values are remarkably high for randomly oriented CNT networks, roughly seven times that of single-walled CNT films. The enhanced thermal conduction is due to the additional wall, which likely gives rise to additional heat-carrying phonon modes and provides a certain resilience to defects. Our results demonstrate that free-standing double-walled CNT films efficiently dissipate heat, enhancing our understanding of these promising films and how they are suited to applications in EUV lithography.

Engineering Wafer-Scale Epitaxial Two-Dimensional Materials through Sapphire Template Screening for Advanced High-Performance Nanoelectronics.

In view of its epitaxial seeding capability, c-plane single crystalline sapphire represents one of the most enticing, industry-compatible templates to realize manufacturable deposition of single crystalline two-dimensional transition metal dichalcogenides (MX2) for functional, ultrascaled, nanoelectronic devices beyond silicon. Despite sapphire being atomically flat, the surface topography, structure, and chemical termination vary between sapphire terraces during the fabrication process. To date, it remains poorly understood how these sapphire surface anomalies affect the local epitaxial registry and the intrinsic electrical properties of the deposited MX2 monolayer. Therefore, molybdenum disulfide (MoS2) is deposited by metal-organic chemical vapor deposition (MOCVD) in an industry-standard epitaxial reactor on two types of c-plane sapphire with distinctly different terrace and step dimensions. Complementary scanning probe microscopy techniques reveal an inhomogeneous conductivity profile in the first epitaxial MoS2 monolayer on both sapphire templates. MoS2 regions with poor conductivity correspond to sapphire terraces with uncontrolled topography and surface structure. By intentionally applying a substantial off-axis cut angle (1° in this work), the sapphire terrace width and step height-and thus also surface structure-become more uniform across the substrate and MoS2 conducts the current more homogeneously. Moreover, these effects propagate into the extrinsic MoS2 device performance: the field-effect transistor variability reduces both within and across wafers at higher median electron mobility. Carefully controlling the sapphire surface topography and structure proves an essential prerequisite to systematically study and control the MX2 growth behavior and capture the influence on its structural and electrical properties.

Understanding ambipolar transport in MoS2 field effect transistors: the substrate is the key.

2D materials offer a pathway for further scaling of CMOS technology. However, for this to become a reality, both n-MOS and p-MOS should be realized, ideally with the same (standard) material. In the specific case of MoS2 field effect transistors (FETs), ambipolar transport is seldom reported, primarily due to the phenomenon of Fermi level pinning (FLP). In this study we identify the possible sources of FLP in MoS2 FETs and resolve them individually. A novel contact transfer technique is used to transfer contacts on top of MoS2 flake devices that results in a significant increase in the hole branch of the transfer characteristics as compared to conventionally fabricated contacts. We hypothesize that the pinning not only comes from the contact-MoS2 interface, but also from the MoS2-substrate interface. We confirm this by shifting to an hBN substrate which leads to a 10 fold increase in the hole current compared to the SiO2 substrate. Furthermore, we analyse MoS2 FETs of different channel thickness on three different substrates, SiO2, hBN and Al2O3, by correlating the p-branch I ON/I OFF to the position of oxide defect band in these substrates. FLP from the oxide is reduced in the case of Al2O3 which enables us to observe ambipolar transport in a bilayer MoS2 FET. These results highlight that MoS2 is indeed an ambipolar material, and the absence of ambipolar transport in MoS2 FETs is strongly correlated to its dielectric environment and processing conditions.

5 × 25 Gbit/s WDM transmitters based on passivated graphene-silicon electro-absorption modulators.

Today, one of the key challenges of graphene devices is establishing fabrication processes that can ensure performance stability and repeatability and that can eventually enable production in high volumes. In this paper, we use up-scalable fabrication processes to demonstrate three five-channel wavelength-division multiplexing (WDM) transmitters, each based on five graphene-silicon electro-absorption modulators. A passivation-first approach is used to encapsulate graphene, which results in hysteresis-free and uniform performance across the five channels of each WDM transmitter, for a total of 15 modulators. Open-eye diagrams are obtained at 25 Gb/s using $ 2.5\;{{\rm V}_{{\rm pp}}} $2.5Vpp, thus demonstrating potential for multi-channel data transmission at ${5}\times {25}\;{\rm Gb/s}$5×25Gb/s on each of the three WDM transmitters.

Importance of the substrate's surface evolution during the MOVPE growth of 2D-transition metal dichalcogenides.

In this paper, we explore the impact of changing the growth conditions on the substrate surface during the metal-organic vapor phase epitaxy of 2D-transition metal dichalcogenides. We particularly study the growth of molybdenum disulfide (MoS2) on sapphire substrates at different temperatures. We show that a high temperature leads to a perfect epitaxial alignment of the MoS2 layer with respect to the sapphire substrate underneath, whereas a low temperature growth induces a 30° epitaxial alignment. This behavior is found to be related to the different sapphire top surface re-arrangement under H2S environment at different growth temperatures. Structural analyses conducted on the different samples confirm an improved layer quality at high temperatures. MoS2 channel-based metal-oxide-semiconductor field-effect transistors are fabricated showing improved device performance with channel layers grown at high temperature.

Material-Selective Doping of 2D TMDC through AlxOy Encapsulation.

For the integration of two-dimensional (2D) transition metal dichalcogenides (TMDC) with high-performance electronic systems, one of the greatest challenges is the realization of doping and comprehension of its mechanisms. Low-temperature atomic layer deposition of aluminum oxide is found to n-dope MoS2 and ReS2 but not WS2. Based on electrical, optical, and chemical analyses, we propose and validate a hypothesis to explain the doping mechanism. Doping is ascribed to donor states in the band gap of AlxOy, which donate electrons or not, based on the alignment of the electronic bands of the 2D TMDC. Through systematic experimental characterization, incorporation of impurities (e.g., carbon) is identified as the likely cause of such states. By modulating the carbon concentration in the capping oxide, doping can be controlled. Through systematic and comprehensive experimental analysis, this study correlates, for the first time, 2D TMDC doping to the carbon incorporation on dielectric encapsulation layers. We highlight the possibility to engineer dopant layers to control the material selectivity and doping concentration in 2D TMDC.

Graphene and two-dimensional materials for silicon technology.

The development of silicon semiconductor technology has produced breakthroughs in electronics-from the microprocessor in the late 1960s to early 1970s, to automation, computers and smartphones-by downscaling the physical size of devices and wires to the nanometre regime. Now, graphene and related two-dimensional (2D) materials offer prospects of unprecedented advances in device performance at the atomic limit, and a synergistic combination of 2D materials with silicon chips promises a heterogeneous platform to deliver massively enhanced potential based on silicon technology. Integration is achieved via three-dimensional monolithic construction of multifunctional high-rise 2D silicon chips, enabling enhanced performance by exploiting the vertical direction and the functional diversification of the silicon platform for applications in opto-electronics and sensing. Here we review the opportunities, progress and challenges of integrating atomically thin materials with silicon-based nanosystems, and also consider the prospects for computational and non-computational applications.

Strongly Hole-Doped and Highly Decoupled Graphene on Platinum by Water Intercalation.

Scanning tunneling microscopy and spectroscopy experiments under ultrahigh vacuum and low-temperature conditions have been performed on water-intercalated graphene on Pt(111). We find that the confined water layer, with a thickness around 0.35 nm, induces a strong hole doping in graphene, i.e., the Dirac point locates at round 0.64 eV above the Fermi level. This can be explained by the presence of a single "puckered bilayer" of ice-Ih, which has not been experimentally found on bare Pt(111), being confined in between graphene and Pt(111) surface. Moreover, the water intercalation makes graphene highly decoupled from the substrate, allowing us to reveal the intrinsic graphene phonons and double Rydberg series of even and odd symmetry image-potential states. Our work not only demonstrates that the electronic properties of graphene can be tuned by the confined water layer between graphene and the substrate, but also provides a generally applicable method to study the intrinsic properties of graphene as well as of other supported two-dimensional materials.

Layer-controlled epitaxy of 2D semiconductors: bridging nanoscale phenomena to wafer-scale uniformity.

The rapid cadence of MOSFET scaling is stimulating the development of new technologies and accelerating the introduction of new semiconducting materials as silicon alternative. In this context, 2D materials with a unique layered structure have attracted tremendous interest in recent years, mainly motivated by their ultra-thin body nature and unique optoelectronic and mechanical properties. The development of scalable synthesis techniques is obviously a fundamental step towards the development of a manufacturable technology. Metal-organic chemical vapor deposition has recently been used for the synthesis of large area TMDs, however, an important milestone still needs to be achieved: the ability to precisely control the number of layers and surface uniformity at the nano-to micro-length scale to obtain an atomically flat, self-passivated surface. In this work, we explore various fundamental aspects involved in the chemical vapor deposition process and we provide important insights on the layer-dependence of epitaxial MoS2 film's structural properties. Based on these observations, we propose an original method to achieve a layer-controlled epitaxy of wafer-scale TMDs.

Graphene delamination using 'electrochemical methods': an ion intercalation effect.

The mechanism of graphene delamination from a Pt catalyst growth surface with electrochemical methods is studied. After a water intercalation step, an electrochemical graphene delamination process is done with a variety of different electrolytes. It is shown that (hydrogen or oxygen) bubble formation is not the main driving force to decouple graphene from its catalyst growth substrate. Ion intercalation is identified as the primary component for a fast graphene delamination process from its catalytic growth substrate. When the Pt/graphene sample is negatively charged, cations will intercalate, assuming they do not reduce within the electrochemical window of the solvent. This cation intercalation does result in graphene delamination. In the same way, anions intercalate in positively charged Pt/graphene samples when they do not react within the electrochemical window of the solvent. Furthermore, it is shown that applying a potential is sufficient (current is not needed) to induce ion intercalation and, as a result, graphene delamination. These findings open the door to avoid Na+ or K+ contamination introduced during currently described electrochemical graphene delamination. Alternative electrolytes (i.e. ammonium hydroxide and tetraethylammonium hydroxide) are proposed, due to the absence of alkali contaminants and rapid cation intercalation to delaminate graphene.

Controlling Water Intercalation Is Key to a Direct Graphene Transfer.

The key steps of a transfer of two-dimensional (2D) materials are the delamination of the as-grown material from a growth substrate and the lamination of the 2D material on a target substrate. In state-of-the-art transfer experiments, these steps remain very challenging, and transfer variations often result in unreliable 2D material properties. Here, it is demonstrated that interfacial water can insert between graphene and its growth substrate despite the hydrophobic behavior of graphene. It is understood that interfacial water is essential for an electrochemistry-based graphene delamination from a Pt surface. Additionally, the lamination of graphene to a target wafer is hindered by intercalation effects, which can even result in graphene delamination from the target wafer. For circumvention of these issues, a direct, support-free graphene transfer process is demonstrated, which relies on the formation of interfacial water between graphene and its growth surface, while avoiding water intercalation between graphene and the target wafer by using hydrophobic silane layers on the target wafer. The proposed direct graphene transfer also avoids polymer contamination (no temporary support layer) and eliminates the need for etching of the catalyst metal. Therefore, recycling of the growth template becomes feasible. The proposed transfer process might even open the door for the suggested atomic-scale interlocking-toy-brick-based stacking of different 2D materials, which will enable a more reliable fabrication of van der Waals heterostructure-based devices and applications.

From the metal to the channel: a study of carrier injection through the metal/2D MoS2 interface.

Despite the fact that two-dimensional MoS2 films continue to be of interest for novel device concepts and beyond silicon technologies, there is still a lack of understanding on the carrier injection at metal/MoS2 interface and effective mitigation of the contact resistance. In this work, we develop a semi-classical model to identify the main mechanisms and trajectories for carrier injection at MoS2 contacts. The proposed model successfully captures the experimentally observed contact behavior and the overall electrical behavior of MoS2 field effect transistors. Using this model, we evaluate the injection trajectories for different MoS2 thicknesses and bias conditions. We find for multilayer (>2) MoS2, the contribution of injection at the contact edge and injection under the contact increase with lateral and perpendicular fields, respectively. Furthermore, we identify that the carriers are predominantly injected at the edge of the contact metal for monolayer and bilayer MoS2. Following these insights, we have found that the transmission line model could significantly overestimate the transfer length and hence the contact resistivity for monolayer and bilayer MoS2. Finally, we evaluate different contact strategies to improve the contact resistance considering the limiting injection trajectory.

Two-dimensional WS2 nanoribbon deposition by conversion of pre-patterned amorphous silicon.

We present a method for area selective deposition of 2D WS2 nanoribbons with tunable thickness on a dielectric substrate. The process is based on a complete conversion of a pre-patterned, H-terminated Si layer to metallic W by WF6, followed by in situ sulfidation by H2S. The reaction process, performed at 450 °C, yields nanoribbons with lateral dimension down to 20 nm and with random basal plane orientation. The thickness of the nanoribbons is accurately controlled by the thickness of the pre-deposited Si layer. Upon rapid thermal annealing at 900 °C under inert gas, the WS2 basal planes align parallel to the substrate.

Highly efficient and stable MoS2 FETs with reversible n-doping using a dehydrated poly(vinyl-alcohol) coating.

Despite rapid progress in 2D molybdenum disulfide (MoS2) research in recent years, MoS2 field-effect transistors (FETs) still suffer from a high metal-to-MoS2 contact resistance and low intrinsic mobility, which are major hindrances to their future application. We report an efficient technique to dope thin-film MoS2 FETs using a poly(vinyl-alcohol) (PVA) polymeric coating. This results in a reduction of the contact resistance by up to 30% as well as a reduction in the channel resistance to 20 kΩ sq-1. Using a dehydration process, we were able to effectively control the surface interactions between MoS2 and the more electropositive hydroxyl groups (-OH) of PVA, which provided a controllable and yet reversible increase in the charge carrier density to a value of 8.0 × 1012 cm-2. The non-covalent, thus non-destructive, PVA doping of MoS2 increases the carrier concentration without degrading the mobility, which shows a monotonic increase while enhancing the doping effect. The PVA doping technique is then exploited to create heavily doped access regions to the intrinsic MoS2 channel, which yields 200% increase of the ON-state source-drain current. This establishes PVA doping as an effective approach to enhance the transport properties of MoS2 FETs for a variety of applications.

Tunable doping of graphene by using physisorbed self-assembled networks.

One current key challenge in graphene research is to tune its charge carrier concentration, i.e., p- and n-type doping of graphene. An attractive approach in this respect is offered by controlled doping via well-ordered self-assembled networks physisorbed on the graphene surface. We report on tunable n-type doping of graphene using self-assembled networks of alkyl-amines that have varying chain lengths. The doping magnitude is modulated by controlling the density of the strong n-type doping amine groups on the surface. As revealed by scanning tunneling and atomic force microscopy, this density is governed by the length of the alkyl chain which acts as a spacer within the self-assembled network. The modulation of the doping magnitude depending on the chain length was demonstrated using Raman spectroscopy and electrical measurements on graphene field effect devices. This supramolecular functionalization approach offers new possibilities for controlling the properties of graphene and other two-dimensional materials at the nanoscale.

High Cycling Stability and Extreme Rate Performance in Nanoscaled LiMn2O4 Thin Films.

Ultrathin LiMn2O4 electrode layers with average crystal size of ∼15 nm were fabricated by means of radio frequency sputtering. Cycling behavior and rate performance was evaluated by galvanostatic charge and discharge measurements. The thinnest films show the highest volumetric capacity and best cycling stability, retaining the initial capacity over 70 (dis)charging cycles when manganese dissolution is prevented. The increased stability for film thicknesses below 50 nm allows cycling in both the 4 and 3 V potential regions, resulting in a high volumetric capacity of 1.2 Ah/cm3. It is shown that the thinnest films can be charged to 75% of their full capacity within 18 s (200 C), the best rate performance reported for LiMn2O4. This is explained by the short diffusion lengths inherent to thin films and the absence of phase transformation.

Graphene oxide monolayers as atomically thin seeding layers for atomic layer deposition of metal oxides.

Graphene oxide (GO) was explored as an atomically-thin transferable seed layer for the atomic layer deposition (ALD) of dielectric materials on any substrate of choice. This approach does not require specific chemical groups on the target surface to initiate ALD. This establishes GO as a unique interface which enables the growth of dielectric materials on a wide range of substrate materials and opens up numerous prospects for applications. In this work, a mild oxygen plasma treatment was used to oxidize graphene monolayers with well-controlled and tunable density of epoxide functional groups. This was confirmed by synchrotron-radiation photoelectron spectroscopy. In addition, density functional theory calculations were carried out on representative epoxidized graphene monolayer models to correlate the capacitive properties of GO with its electronic structure. Capacitance-voltage measurements showed that the capacitive behavior of Al2O3/GO depends on the oxidation level of GO. Finally, GO was successfully used as an ALD seed layer for the deposition of Al2O3 on chemically inert single layer graphene, resulting in high performance top-gated field-effect transistors.