Manufacture and characterization of graphene membranes with suspended silicon proof masses for MEMS and NEMS applications.

Graphene's unparalleled strength, chemical stability, ultimate surface-to-volume ratio and excellent electronic properties make it an ideal candidate as a material for membranes in micro- and nanoelectromechanical systems (MEMS and NEMS). However, the integration of graphene into MEMS or NEMS devices and suspended structures such as proof masses on graphene membranes raises several technological challenges, including collapse and rupture of the graphene. We have developed a robust route for realizing membranes made of double-layer CVD graphene and suspending large silicon proof masses on membranes with high yields. We have demonstrated the manufacture of square graphene membranes with side lengths from 7 µm to 110 µm, and suspended proof masses consisting of solid silicon cubes that are from 5 µm × 5 µm × 16.4 µm to 100 µm × 100 µm × 16.4 µm in size. Our approach is compatible with wafer-scale MEMS and semiconductor manufacturing technologies, and the manufacturing yields of the graphene membranes with suspended proof masses were >90%, with >70% of the graphene membranes having >90% graphene area without visible defects. The measured resonance frequencies of the realized structures ranged from tens to hundreds of kHz, with quality factors ranging from 63 to 148. The graphene membranes with suspended proof masses were extremely robust, and were able to withstand indentation forces from an atomic force microscope (AFM) tip of up to ~7000 nN. The proposed approach for the reliable and large-scale manufacture of graphene membranes with suspended proof masses will enable the development and study of innovative NEMS devices with new functionalities and improved performances.

Suspended Graphene Membranes with Attached Silicon Proof Masses as Piezoresistive Nanoelectromechanical Systems Accelerometers.

Graphene is an atomically thin material that features unique electrical and mechanical properties, which makes it an extremely promising material for future nanoelectromechanical systems (NEMS). Recently, basic NEMS accelerometer functionality has been demonstrated by utilizing piezoresistive graphene ribbons with suspended silicon proof masses. However, the proposed graphene ribbons have limitations regarding mechanical robustness, manufacturing yield, and the maximum measurement current that can be applied across the ribbons. Here, we report on suspended graphene membranes that are fully clamped at their circumference and have attached silicon proof masses. We demonstrate their utility as piezoresistive NEMS accelerometers, and they are found to be more robust, have longer life span and higher manufacturing yield, can withstand higher measurement currents, and are able to suspend larger silicon proof masses, as compared to the previous graphene ribbon devices. These findings are an important step toward bringing ultraminiaturized piezoresistive graphene NEMS closer toward deployment in emerging applications such as in wearable electronics, biomedical implants, and internet of things (IoT) devices.

Fully inkjet printed ultrathin microsupercapacitors based on graphene electrodes and a nano-graphene oxide electrolyte.

The advance of miniaturized and low-power electronics has a striking impact on the development of energy storage devices with constantly tougher constraints in terms of form factor and performance. Microsupercapacitors (MSCs) are considered a potential solution to this problem, thanks to their compact device structure. Great efforts have been made to maximize their performance with new materials like graphene and to minimize their production cost with scalable fabrication processes. In this regard, we developed a full inkjet printing process for the production of all-graphene microsupercapacitors with electrodes based on electrochemically exfoliated graphene and an ultrathin solid-state electrolyte based on nano-graphene oxide. The devices exploit the high ionic conductivity of nano-graphene oxide coupled with the high electrical conductivity of graphene films, yielding areal capacitances of up to 313 µF cm-2 at 5 mV s-1 and high power densities of up to ∼4 mW cm-3 with an overall device thickness of only ∼1 µm.

Influence of Humidity on Contact Resistance in Graphene Devices.

The electrical contact resistance at metal-graphene interfaces can significantly degrade the properties of graphene devices and is currently hindering the full exploitation of graphene's potential. Therefore, the influence of environmental factors, such as humidity, on the metal-graphene contact resistance is of interest for all graphene devices that operate without hermetic packaging. We experimentally studied the influence of humidity on bottom-contacted chemical-vapor-deposited (CVD) graphene-gold contacts, by extracting the contact resistance from transmission line model (TLM) test structures. Our results indicate that the contact resistance is not significantly affected by changes in relative humidity (RH). This behavior is in contrast to the measured humidity sensitivity [Formula: see text] of graphene's sheet resistance. In addition, we employ density functional theory (DFT) simulations to support our experimental observations. Our DFT simulation results demonstrate that the electronic structure of the graphene sheet on top of silica is much more sensitive to adsorbed water molecules than the charge density at the interface between gold and graphene. Thus, we predict no degradation of device performance by alterations in contact resistance when such contacts are exposed to humidity. This knowledge underlines that bottom-contacting of graphene is a viable approach for a variety of graphene devices and the back end of the line integration on top of conventional integrated circuits.

Monolithic Wafer Scale Integration of Silicon Nanoribbon Sensors with CMOS for Lab-on-Chip Application.

Silicon ribbons (SiRi) have been well-established as highly sensitive transducers for biosensing applications thanks to their high surface to volume ratio. However, selective and multiplexed detection of biomarkers remains a challenge. Further, very few attempts have been made to integrate SiRi with complementary-metal-oxide-semiconductor (CMOS) circuits to form a complete lab-on-chip (LOC). Integration of SiRi with CMOS will facilitate real time detection of the output signal and provide a compact small sized LOC. Here, we propose a novel pixel based SiRi device monolithically integrated with CMOS field-effect-transistors (FET) for real-time selective multiplexed detection. The SiRi pixels are fabricated on a silicon-on-insulator wafer using a top-down method. Each pixel houses a control FET, fluid-gate (FG) and SiRi sensor. The pixel is controlled by simultaneously applying frontgate (VG) and backgate voltage (VBG). The liquid potential can be monitored using the FG. We report the transfer characteristics (ID-VG) of N- and P-type SiRi pixels. Further, the ID-VG characteristics of the SiRis are studied at different VBG. The application of VBG to turn ON the SiRi modulates the subthreshold slope (SS) and threshold voltage (VTH) of the control FET. Particularly, N-type pixels cannot be turned OFF due to the control NFET operating in the strong inversion regime. This is due to large VBG (≥25 V) application to turn ON the SiRi sensor. Conversely, the P-type SiRi sensors do not require large VBG to switch ON. Thus, P-type pixels exhibit excellent ION/IOFF ≥ 106, SS of 70⁻80 mV/dec and VTH of 0.5 V. These promising results will empower the large-scale cost-efficient production of SiRi based LOC sensors.

Scalable Fabrication and Integration of Graphene Microsupercapacitors through Full Inkjet Printing.

A simple full-inkjet-printing technique is developed for the scalable fabrication of graphene-based microsupercapacitors (MSCs) on various substrates. High-performance graphene inks are formulated by integrating the electrochemically exfoliated graphene with a solvent exchange technique to reliably print graphene interdigitated electrodes with tunable geometry and thickness. Along with the printed polyelectrolyte, poly(4-styrenesulfonic acid), the fully printed graphene-based MSCs attain the highest areal capacitance of ∼0.7 mF/cm2, substantially advancing the state-of-art of all-solid-state MSCs with printed graphene electrodes. The full printing solution enables scalable fabrication of MSCs and effective connection of them in parallel and/or in series at various scales. Remarkably, more than 100 devices have been connected to form large-scale MSC arrays as power banks on both silicon wafers and Kapton. Without any extra protection or encapsulation, the MSC arrays can be reliably charged up to 12 V and retain the performance even 8 months after fabrication.

Inkjet printed highly transparent and flexible graphene micro-supercapacitors.

Modern energy storage devices for portable and wearable technologies must fulfill a number of requirements, such as small size, flexibility, thinness, reliability, transparency, manufacturing simplicity and performance, in order to be competitive in an ever expanding market. To this end, a comprehensive inkjet printing process is developed for the scalable and low-cost fabrication of transparent and flexible micro-supercapacitors. These solid-state devices, with printed thin films of graphene flakes as interdigitated electrodes, exhibit excellent performance versus transparency (ranging from a single-electrode areal capacitance of 16 µF cm-2 at transmittance of 90% to a capacitance of 99 µF cm-2 at transmittance of 71%). Also, transparent and flexible devices are fabricated, showing negligible capacitance degradation during bending. The ease of manufacturing coupled with their great capacitive properties opens up new potential applications for energy storage devices ranging from portable solar cells to wearable sensors.

Noninvasive Scanning Raman Spectroscopy and Tomography for Graphene Membrane Characterization.

Graphene has extraordinary mechanical and electronic properties, making it a promising material for membrane-based nanoelectromechanical systems (NEMS). Here, chemical-vapor-deposited graphene is transferred onto target substrates to suspend it over cavities and trenches for pressure-sensor applications. The development of such devices requires suitable metrology methods, i.e., large-scale characterization techniques, to confirm and analyze successful graphene transfer with intact suspended graphene membranes. We propose fast and noninvasive Raman spectroscopy mapping to distinguish between free-standing and substrate-supported graphene, utilizing the different strain and doping levels. The technique is expanded to combine two-dimensional area scans with cross-sectional Raman spectroscopy, resulting in three-dimensional Raman tomography of membrane-based graphene NEMS. The potential of Raman tomography for in-line monitoring is further demonstrated with a methodology for automated data analysis to spatially resolve the material composition in micrometer-scale integrated devices, including free-standing and substrate-supported graphene. Raman tomography may be applied to devices composed of other two-dimensional materials as well as silicon micro- and nanoelectromechanical systems.

Piezoresistive Properties of Suspended Graphene Membranes under Uniaxial and Biaxial Strain in Nanoelectromechanical Pressure Sensors.

Graphene membranes act as highly sensitive transducers in nanoelectromechanical devices due to their ultimate thinness. Previously, the piezoresistive effect has been experimentally verified in graphene using uniaxial strain in graphene. Here, we report experimental and theoretical data on the uni- and biaxial piezoresistive properties of suspended graphene membranes applied to piezoresistive pressure sensors. A detailed model that utilizes a linearized Boltzman transport equation describes accurately the charge-carrier density and mobility in strained graphene and, hence, the gauge factor. The gauge factor is found to be practically independent of the doping concentration and crystallographic orientation of the graphene films. These investigations provide deeper insight into the piezoresistive behavior of graphene membranes.

Resistive graphene humidity sensors with rapid and direct electrical readout.

We demonstrate humidity sensing using a change of the electrical resistance of single-layer chemical vapor deposited (CVD) graphene that is placed on top of a SiO2 layer on a Si wafer. To investigate the selectivity of the sensor towards the most common constituents in air, its signal response was characterized individually for water vapor (H2O), nitrogen (N2), oxygen (O2), and argon (Ar). In order to assess the humidity sensing effect for a range from 1% relative humidity (RH) to 96% RH, the devices were characterized both in a vacuum chamber and in a humidity chamber at atmospheric pressure. The measured response and recovery times of the graphene humidity sensors are on the order of several hundred milliseconds. Density functional theory simulations are employed to further investigate the sensitivity of the graphene devices towards water vapor. The interaction between the electrostatic dipole moment of the water and the impurity bands in the SiO2 substrate leads to electrostatic doping of the graphene layer. The proposed graphene sensor provides rapid response direct electrical readout and is compatible with back end of the line (BEOL) integration on top of CMOS-based integrated circuits.

Residual metallic contamination of transferred chemical vapor deposited graphene.

Integration of graphene with Si microelectronics is very appealing by offering a potentially broad range of new functionalities. New materials to be integrated with the Si platform must conform to stringent purity standards. Here, we investigate graphene layers grown on copper foils by chemical vapor deposition and transferred to silicon wafers by wet etching and electrochemical delamination methods with respect to residual submonolayer metallic contaminations. Regardless of the transfer method and associated cleaning scheme, time-of-flight secondary ion mass spectrometry and total reflection X-ray fluorescence measurements indicate that the graphene sheets are contaminated with residual metals (copper, iron) with a concentration exceeding 10(13) atoms/cm(2). These metal impurities appear to be partially mobile upon thermal treatment, as shown by depth profiling and reduction of the minority charge carrier diffusion length in the silicon substrate. As residual metallic impurities can significantly alter electronic and electrochemical properties of graphene and can severely impede the process of integration with silicon microelectronics, these results reveal that further progress in synthesis, handling, and cleaning of graphene is required to advance electronic and optoelectronic applications.

Conductivity scaling in supercritical percolation of nanoparticles--not a power law.

The power-law behavior widely observed in supercritical percolation systems of conductive nanoparticles may merely be a phenomenological approximation to the true scaling law not yet discovered. In this work, we derive a comprehensive yet simple scaling law and verify its extensive applicability to various experimental and numerical systems. In contrast to the power law which lacks theoretical backing, the new scaling law is explanatory and predictive, and thereby helpful to gain more new insights into percolation systems of conductive nanoparticles.

Inkjet printing of 2D layered materials.

Inkjet printing of 2D layered materials, such as graphene and MoS2, has attracted great interests for emerging electronics. However, incompatible rheology, low concentration, severe aggregation and toxicity of solvents constitute critical challenges which hamper the manufacturing efficiency and product quality. Here, we introduce a simple and general technology concept (distillation-assisted solvent exchange) to efficiently overcome these challenges. By implementing the concept, we have demonstrated excellent jetting performance, ideal printing patterns and a variety of promising applications for inkjet printing of 2D layered materials.

Percolation thresholds of two-dimensional continuum systems of rectangles.

The present paper introduces an efficient Monte Carlo algorithm for continuum percolation composed of randomly oriented rectangles. By conducting extensive simulations, we report high-precision percolation thresholds for a variety of homogeneous systems with different rectangle aspect ratios. This paper verifies and extends the excluded area theory. It is confirmed that percolation thresholds are dominated by the average excluded areas for both homogeneous and heterogeneous rectangle systems (except for some special heterogeneous systems where the rectangle lengths differ too much from one another). In terms of the excluded areas, generalized formulas are proposed to effectively predict precise percolation thresholds for all these rectangle systems. This paper is, therefore, helpful for both practical applications and theoretical studies concerning relevant systems.

Efficient inkjet printing of graphene.

An efficient and mature inkjet printing technology is introduced for mass production of coffee-ring-free patterns of high-quality graphene at high resolution (unmarked scale bars are 100 µm). Typically, several passes of printing and a simple baking allow fabricating a variety of good-performance electronic devices, including transparent conductors, embedded resistors, thin film transistors, and micro-supercapacitors.

A graphene-based hot electron transistor.

We experimentally demonstrate DC functionality of graphene-based hot electron transistors, which we call graphene base transistors (GBT). The fabrication scheme is potentially compatible with silicon technology and can be carried out at the wafer scale with standard silicon technology. The state of the GBTs can be switched by a potential applied to the transistor base, which is made of graphene. Transfer characteristics of the GBTs show ON/OFF current ratios exceeding 10(4).

Corrected finite-size scaling in percolation.

This Rapid Communication proposes a comprehensive scaling theory for percolation, which clarifies the intrinsic nature of finite-size scaling and effectively addresses the finite-size effects. This theory applies to extensive systems, including especially the explosive percolation. It is suggested that explosive percolation shares the same scaling law as normal percolation, but may suffer from more severe finite-size effects. Remarkably, in contrast to previous studies, relying on the framework of our theory, the present Rapid Communication suggests that for all systems, the universal scaling functions do not depend on the boundary conditions.

Threshold of hierarchical percolating systems.

Many modern nanostructured materials and doped polymers are morphologically too complex to be interpreted by classical percolation theory. Here, we develop the concept of a hierarchical percolating (percolation-within-percolation) system to describe such complex materials and illustrate how to generalize the conventional percolation to double-level percolation. Based on Monte Carlo simulations, we find that the double-level percolation threshold is close to, but definitely larger than, the product of the local percolation thresholds for the two enclosed single-level systems. The deviation may offer alternative insights into physics concerning infinite clusters and open up new research directions for percolation theory.

Impact of oxidation and reduction annealing on the electrical properties of Ge/La2O3/ZrO2 gate stacks.

The paper addresses the passivation of Germanium surfaces by using layered La2O3/ZrO2 high-k dielectrics deposited by Atomic Layer Deposition to be applied in Ge-based MOSFET devices. Improved electrical properties of these multilayered gate stacks exposed to oxidizing and reducing ambient during thermal post treatment in presence of thin Pt cap layers are demonstrated. The results suggest the formation of thin intermixed La x Ge y O z interfacial layers with thicknesses controllable by oxidation time. This formation is further investigated by XPS, EDX/EELS and TEM analysis. An additional reduction annealing treatment further improves the electrical properties of the gate dielectrics in contact with the Ge substrate. As a result low interface trap densities on (1 0 0) Ge down to 3 × 1011 eV-1 cm-2 are demonstrated. The formation of the high-k La x Ge y O z layer is in agreement with the oxide densification theory and may explain the improved interface trap densities. The scaling potential of the respective layered gate dielectrics used in Ge-based MOS-based device structures to EOT of 1.2 nm or below is discussed. A trade-off between improved interface trap density and a lowered equivalent oxide thickness is found.