The sensitivity enhancement of TiO2-based VOCs sensor decorated by gold at room temperature.

Detection of hazardous toxic gases for air pollution monitoring and medical diagnosis has attracted the attention of researchers in order to realize sufficiently sensitive gas sensors. In this paper, we fabricated and characterized a Titanium dioxide (TiO2)-based gas sensor enhanced using the gold nanoparticles. Thermal oxidation and sputter deposition methods were used to synthesize fabricated gas sensor. X-ray diffraction analysis was used to determine the anatase structure of TiO2samples. It was found that the presence of gold nanoparticles on the surface of TiO2enhances the sensitivity response of gas sensors by up to about 40%. The fabricated gas sensor showed a sensitivity of 1.1, 1.07 and 1.03 to 50 ppm of acetone, methanol and ethanol vapors at room temperature, respectively. Additionally, the gold nanoparticles reduce 50 s of response time (about 50% reduction) in the presence of 50 ppm ethanol vapor; and we demonstrated that the recovery time of the gold decorated TiO2sensor is less than 40 s. Moreover, we explain that the improved performance depends on the adsorption-desorption mechanism, and the chemical sensitization and electronic sensitization of gold nanoparticles.

Mass and density determination of porous nanoparticle films using a quartz crystal microbalance.

A method is presented to directly measure the mass output of an impaction printer coupled with a spark ablation generator. It is based on a quartz crystal microbalance and shown to be reliable in quantifying mass deposition rate. Here, the method is demonstrated with an Au nanoparticle aerosol synthesized under several spark ablation and deposition settings. Changes in the deposition rate in response to changed synthesis conditions follow the spark ablation models on generation rate made in previous studies, validating this novel measurement method. In combination with the volume of a deposit, a good estimate of the film porosity can be made. The Au nanoparticle films synthesized here have a low porosity of 0.18 due to extensive restructuring and compaction on impact with the substrate. The porosity is found to be insensitive to deposition settings and is constant throughout the film. The simplicity and low cost of a quartz crystal microbalance setup make this an accessible method to determine porosity in porous thin films.

Effect of temperature and humidity on the sensing performance of TiO2nanowire-based ethanol vapor sensors.

In this paper, we study the influence of two key factors, temperature, and humidity, on gas sensors based on titanium dioxide nanowires synthesized at 4 different temperatures and with different morphology. The samples' structure are investigated using SEM, XRD and FTIR analysis. The effects of humidity and temperature are studied by measuring the resistance and gas response when exposed to ethanol. At room temperature, we observed a 15% sensitivity response to 100 ppm of ethanol vapor and by increasing the operating temperature up to 180 °C, the response is enhanced by two orders of magnitude. The best operating temperature for the highest gas response is found to be around 180 °C. Also, it was observed that every nanowire morphology has its own optimum operating temperature. The resistance of sensors is increased at higher Relative Humidity (RH). Besides, the response to ethanol vapor experiences a gradual increase when the RH rises from 10% to 60%. On the other hand, from 60% to 90% RH the gas response decreases gradually due to different mechanisms of interaction of the TiO2with H2O and ethanol molecules.

Multi-layer graphene pirani pressure sensors.

The operating principle of Pirani pressure sensors is based on the pressure dependence of a suspended strip's electrical conductivity, caused by the thermal conductance of the surrounding gas which changes the Joule heating of the strip. To realize such sensors, not only materials with high temperature dependent electrical conductivity are required, but also minimization of the suspended strip dimensions is essential to maximize the responsivity and minimize the power consumption. Due to this, nanomaterials are especially attractive for this application. Here, we demonstrate the use of a multi-layer suspended graphene strip as a Pirani pressure sensor and compare its behavior with existing models. A clear pressure dependence of the strip's electrical resistance is observed, with a maximum relative change of 2.75% between 1 and 1000 mbar and a power consumption of 8.5 mW. The use of graphene enables miniaturization of the device footprint by 100 times compared to state-of-the-art. Moreover, miniaturization allows for lower power consumption and/or higher responsivity and the sensor's nanogap enables operation near atmospheric pressure that can be used in applications such as barometers for altitude measurement. Furthermore, we demonstrate that the sensor response depends on the type of gas molecules, which opens up the way to selective gas sensing applications. Finally, the graphene synthesis technology is compatible with wafer-scale fabrication, potentially enabling future chip-level integration with readout electronics.

Low-Humidity Sensing Properties of Multi-Layered Graphene Grown by Chemical Vapor Deposition.

Humidity sensing is fundamental in some applications, as humidity can be a strong interferent in the detection of analytes under environmental conditions. Ideally, materials sensitive or insensitive towards humidity are strongly needed for the sensors used in the first or second case, respectively. We present here the sensing properties of multi-layered graphene (MLG) upon exposure to different levels of relative humidity. We synthesize MLG by chemical vapor deposition, as shown by Raman spectroscopy, Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). Through an MLG-based resistor, we show that MLG is scarcely sensitive to humidity in the range 30%-70%, determining current variations in the range of 0.005%/%relative humidity (RH) well below the variation induced by other analytes. These findings, due to the morphological properties of MLG, suggest that defective MLG is the ideal sensing material to implement in gas sensors operating both at room temperature and humid conditions.

Analysis of a calibration method for non-stationary CVD multi-layered graphene-based gas sensors.

Limitations such as lack of detected stationary signal and slow signal recovery after detection currently affect graphene-based chemi-sensors operating at room temperature. In this work, we model the behavior of a sensor in a test chamber having limited volume and simulating the environmental conditions. From this model, we mathematically derive the calibration method for the sensor. The approach, focused on the time differential of the signal output, is tested on multi-layered graphene (MLG)-based sensors towards the chosen target gas (nitrogen dioxide) in the range from 0.12 to 1.32 ppm. MLG acting as sensing layer is synthesized by chemical vapor deposition. Our study paves the route for a wider applicability of the analysis to calibrate the class of devices affected by non-stationary and recovery issues.

Effects of Conformal Nanoscale Coatings on Thermal Performance of Vertically Aligned Carbon Nanotubes.

The high aspect ratio and the porous nature of spatially oriented forest-like carbon nanotube (CNT) structures represent a unique opportunity to engineer a novel class of nanoscale assemblies. By combining CNTs and conformal coatings, a 3D lightweight scaffold with tailored behavior can be achieved. The effect of nanoscale coatings, aluminum oxide (Al2 O3 ) and nonstoichiometric amorphous silicon carbide (a-SiC), on the thermal transport efficiency of high aspect ratio vertically aligned CNTs, is reported herein. The thermal performance of the CNT-based nanostructure strongly depends on the achieved porosity, the coating material and its infiltration within the nanotube network. An unprecedented enhancement in terms of effective thermal conductivity in a-SiC coated CNTs has been obtained: 181% compared to the as-grown CNTs and Al2 O3 coated CNTs. Furthermore, the integration of coated high aspect ratio CNTs in an epoxy molding compound demonstrates that, next to the required thermal conductivity, the mechanical compliance for thermal interface applications can also be achieved through coating infiltration into foam-like CNT forests.

Impact of the atomic layer deposition precursors diffusion on solid-state carbon nanotube based supercapacitors performances.

A study on the impact of atomic layer deposition (ALD) precursors diffusion on the performance of solid-state miniaturized nanostructure capacitor array is presented. Three-dimensional nanostructured capacitor array based on double conformal coating of multiwalled carbon nanotubes (MWCNTs) bundles is realized using ALD to deposit Al2O3 as dielectric layer and TiN as high aspect-ratio conformal counter-electrode on 2 µm long MWCNT bundles. The devices have a small footprint (from 100 µm(2) to 2500 µm(2)) and are realized using an IC wafer-scale manufacturing process with high reproducibility (≤0.3E-12F deviation). To evaluate the enhancement of the electrode surface, the measured capacitance values are compared to a lumped circuital model. The observed discrepancies are explained with a partial coating of the CNT, that determine a limited use of the available electrode surface area. To analyze the CNT coating effectiveness, the ALD precursors diffusions inside the CNT bundle is studied using a Knudsen diffusion mechanism.

A high aspect ratio surface micromachined accelerometer based on a SiC-CNT composite material.

Silicon carbide (SiC) is recognized as an excellent material for microelectromechanical systems (MEMS), especially those operating in challenging environments, such as high temperature, high radiation, and corrosive environments. However, SiC bulk micromachining is still a challenge, which hinders the development of complex SiC MEMS. To address this problem, we present the use of a carbon nanotube (CNT) array coated with amorphous SiC (a-SiC) as an alternative composite material to enable high aspect ratio (HAR) surface micromachining. By using a prepatterned catalyst layer, a HAR CNT array can be grown as a structural template and then densified by uniformly filling the CNT bundle with LPCVD a-SiC. The electrical properties of the resulting SiC-CNT composite were characterized, and the results indicated that the electrical resistivity was dominated by the CNTs. To demonstrate the use of this composite in MEMS applications, a capacitive accelerometer was designed, fabricated, and measured. The fabrication results showed that the composite is fully compatible with the manufacturing of surface micromachining devices. The Young's modulus of the composite was extracted from the measured spring constant, and the results show a great improvement in the mechanical properties of the CNTs after coating with a-SiC. The accelerometer was electrically characterized, and its functionality was confirmed using a mechanical shaker.

Surface modification of multilayer graphene electrodes by local printing of platinum nanoparticles using spark ablation for neural interfacing.

In this paper, we present the surface modification of multilayer graphene electrodes with platinum (Pt) nanoparticles (NPs) using spark ablation. This method yields an individually selective local printing of NPs on an electrode surface at room temperature in a dry process. NP printing is performed as a post-process step to enhance the electrochemical characteristics of graphene electrodes. The NP-printed electrode shows significant improvements in impedance, charge storage capacity (CSC), and charge injection capacity (CIC), versus the equivalent electrodes without NPs. Specifically, electrodes with 40% NP surface density demonstrate 4.5 times lower impedance, 15 times higher CSC, and 4 times better CIC. Electrochemical stability, assessed via continuous cyclic voltammetry (CV) and voltage transient (VT) tests, indicated minimal deviations from the initial performance, while mechanical stability, assessed via ultrasonic vibration, is also improved after the NP printing. Importantly, NP surface densities up to 40% maintain the electrode optical transparency required for compatibility with optical imaging and optogenetics. These results demonstrate selective NP deposition and local modification of electrochemical properties in graphene electrodes for the first time, enabling the cohabitation of graphene electrodes with different electrochemical and optical characteristics on the same substrate for neural interfacing.

Correction: Highly-sensitive wafer-scale transfer-free graphene MEMS condenser microphones.

[This corrects the article DOI: 10.1038/s41378-024-00656-x.].

Highly-sensitive wafer-scale transfer-free graphene MEMS condenser microphones.

Since the performance of micro-electro-mechanical system (MEMS)-based microphones is approaching fundamental physical, design, and material limits, it has become challenging to improve them. Several works have demonstrated graphene's suitability as a microphone diaphragm. The potential for achieving smaller, more sensitive, and scalable on-chip MEMS microphones is yet to be determined. To address large graphene sizes, graphene-polymer heterostructures have been proposed, but they compromise performance due to added polymer mass and stiffness. This work demonstrates the first wafer-scale integrated MEMS condenser microphones with diameters of 2R = 220-320 µm, thickness of 7 nm multi-layer graphene, that is suspended over a back-plate with a residual gap of 5 µm. The microphones are manufactured with MEMS compatible wafer-scale technologies without any transfer steps or polymer layers that are more prone to contaminate and wrinkle the graphene. Different designs, all electrically integrated are fabricated and characterized allowing us to study the effects of the introduction of a back-plate for capacitive read-out. The devices show high mechanical compliances Cm = 0.081-1.07 µmPa-1 (10-100 × higher than the silicon reported in the state-of-the-art diaphragms) and pull-in voltages in the range of 2-9.5 V. In addition, to validate the proof of concept, we have electrically characterized the graphene microphone when subjected to sound actuation. An estimated sensitivity of S1kHz = 24.3-321 mV Pa-1 for a Vbias = 1.5 V was determined, which is 1.9-25.5 × higher than of state-of-the-art microphone devices while having a ~9 × smaller area.

Overview of Engineering Carbon Nanomaterials Such As Carbon Nanotubes (CNTs), Carbon Nanofibers (CNFs), Graphene and Nanodiamonds and Other Carbon Allotropes inside Porous Anodic Alumina (PAA) Templates.

The fabrication and design of carbon-based hierarchical structures with tailored nano-architectures have attracted the enormous attention of the materials science community due to their exceptional chemical and physical properties. The collective control of nano-objects, in terms of their dimensionality, orientation and size, is of paramount importance to expand the implementation of carbon nanomaterials across a large variety of applications. In this context, porous anodic alumina (PAA) has become an attractive template where the pore morphologies can be straightforwardly modulated. The synthesis of diverse carbon nanomaterials can be performed using PAA templates, such as carbon nanotubes (CNTs), carbon nanofibers (CNFs), and nanodiamonds, or can act as support for other carbon allotropes such as graphene and other carbon nanoforms. However, the successful growth of carbon nanomaterials within ordered PAA templates typically requires a series of stages involving the template fabrication, nanostructure growth and finally an etching or electrode metallization steps, which all encounter different challenges towards a nanodevice fabrication. The present review article describes the advantages and challenges associated with the fabrication of carbon materials in PAA based materials and aims to give a renewed momentum to this topic within the materials science community by providing an exhaustive overview of the current synthesis approaches and the most relevant applications based on PAA/Carbon nanostructures materials. Finally, the perspective and opportunities in the field are presented.

Nanostructured Thermoelectric Films Synthesised by Spark Ablation and Their Oxidation Behaviour.

Reducing the thermal conductivity of thermoelectric materials has been a field of intense research to improve the efficiency of thermoelectric devices. One approach is to create a nanostructured thermoelectric material that has a low thermal conductivity due to its high number of grain boundaries or voids, which scatter phonons. Here, we present a new method based on spark ablation nanoparticle generation to create nanostructured thermoelectric materials, demonstrated using Bi2Te3. The lowest achieved thermal conductivity was <0.1 W m-1 K-1 at room temperature with a mean nanoparticle size of 8±2 nm and a porosity of 44%. This is comparable to the best published nanostructured Bi2Te3 films. Oxidation is also shown to be a major issue for nanoporous materials such as the one here, illustrating the importance of immediate, air-tight packaging of such materials after synthesis and deposition.

Ultra-sensitive graphene membranes for microphone applications.

Microphones exploit the motion of suspended membranes to detect sound waves. Since the microphone performance can be improved by reducing the thickness and mass of its sensing membrane, graphene-based microphones are expected to outperform state-of-the-art microelectromechanical (MEMS) microphones and allow further miniaturization of the device. Here, we present a laser vibrometry study of the acoustic response of suspended multilayer graphene membranes for microphone applications. We address performance parameters relevant for acoustic sensing, including mechanical sensitivity, limit of detection and nonlinear distortion, and discuss the trade-offs and limitations in the design of graphene microphones. We demonstrate superior mechanical sensitivities of the graphene membranes, reaching more than 2 orders of magnitude higher compliances than commercial MEMS devices, and report a limit of detection as low as 15 dBSPL, which is 10-15 dB lower than that featured by current MEMS microphones.

Direct Wafer-Scale CVD Graphene Growth under Platinum Thin-Films.

Since the transfer process of graphene from a dedicated growth substrate to another substrate is prone to induce defects and contamination and can increase costs, there is a large interest in methods for growing graphene directly on silicon wafers. Here, we demonstrate the direct CVD growth of graphene on a SiO2 layer on a silicon wafer by employing a Pt thin film as catalyst. We pattern the platinum film, after which a CVD graphene layer is grown at the interface between the SiO2 and the Pt. After removing the Pt, Raman spectroscopy demonstrates the local growth of monolayer graphene on SiO2. By tuning the CVD process, we were able to fully cover 4-inch oxidized silicon wafers with transfer-free monolayer graphene, a result that is not easily obtained using other methods. By adding Ta structures, local graphene growth on SiO2 is selectively blocked, allowing the controlled graphene growth on areas selected by mask design.

Sensitive Transfer-Free Wafer-Scale Graphene Microphones.

During the past decades micro-electromechanical microphones have largely taken over the market for portable devices, being produced in volumes of billions yearly. Because performance of current devices is near the physical limits, further miniaturization and improvement of microphones for mobile devices poses a major challenge that requires breakthrough device concepts, geometries, and materials. Graphene is an attractive material for enabling these breakthroughs due to its flexibility, strength, nanometer thinness, and high electrical conductivity. Here, we demonstrate that transfer-free 7 nm thick multilayer graphene (MLGr) membranes with diameters ranging from 85-155 to 300 µm can be used to detect sound and show a mechanical compliance up to 92 nm Pa-1, thus outperforming commercially available MEMS microphones of 950 µm with compliances around 3 nm Pa-1. The feasibility of realizing larger membranes with diameters of 300 µm and even higher compliances is shown, although these have lower yields. We present a process for locally growing graphene on a silicon wafer and realizing suspended membranes of patterned graphene across through-silicon holes by bulk micromachining and sacrificial layer etching, such that no transfer is required. This transfer-free method results in a 100% yield for membranes with diameters up to 155 µm on 132 fabricated drums. The device-to-device variations in the mechanical compliance in the audible range (20-20000 Hz) are significantly smaller than those in transferred membranes. With this work, we demonstrate a transfer-free method for realizing wafer-scale multilayer graphene membranes that is compatible with high-volume manufacturing. Thus, limitations of transfer-based methods for graphene microphone fabrication such as polymer contamination, crack formation, wrinkling, folding, delamination, and low-tension reproducibility are largely circumvented, setting a significant step on the route toward high-volume production of graphene microphones.

Enhancement of Room Temperature Ethanol Sensing by Optimizing the Density of Vertically Aligned Carbon Nanofibers Decorated with Gold Nanoparticles.

An ethanol gas sensor based on carbon nanofibers (CNFs) with various densities and nanoparticle functionalization was investigated. The CNFs were grown by means of a Plasma-Enhanced Chemical Vapor Deposition (PECVD), and the synthesis conditions were varied to obtain different number of fibers per unit area. The devices with a larger density of CNFs lead to higher responses, with a maximal responsivity of 10%. Furthermore, to simultaneously improve the sensitivity and selectivity, CNFs were decorated with gold nanoparticles by an impaction printing method. After metal decoration, the devices showed a response 300% higher than pristine devices toward 5 ppm of ethanol gas. The morphology and structure of the different samples deposited on a silicon substrate were characterized by TEM, EDX, SEM, and Raman spectroscopy, and the results confirmed the presence of CNF decorated with gold. The influence of operating temperature (OT) and humidity were studied on the sensing devices. In the case of decorated samples with a high density of nanofibers, a less-strong cross-sensitivity was observed toward a variation in humidity and temperature.

Effects of temperature and grain size on diffusivity of aluminium: electromigration experiment and molecular dynamic simulation.

Understanding the atomic diffusion features in metallic material is significant to explain the diffusion-controlled physical processes. In this paper, using electromigration experiments and molecular dynamic (MD) simulations, we investigate the effects of grain size and temperature on the self-diffusion of polycrystalline aluminium (Al). The mass transport due to electromigration are accelerated by increasing temperature and decreasing grain size. Magnitudes of effective diffusivity (Deff) and grain boundary diffusivity (DGBs) are experimentally determined, in which theDeffchanges as a function of grain size and temperature, butDGBsis independent of the grain size, only affected by the temperature. Moreover, MD simulations of atomic diffusion in polycrystalline Al demonstrate those observations from experiments. Based on MD results, the Arrhenius equation ofDGBsand empirical formula of the thickness of grain boundaries at various temperatures are obtained. In total,DeffandDGBsobtained in the present study agree with literature results, and a comprehensive result of diffusivities related to the grain size is presented.

Multilayer CVD graphene electrodes using a transfer-free process for the next generation of optically transparent and MRI-compatible neural interfaces.

Multimodal platforms combining electrical neural recording and stimulation, optogenetics, optical imaging, and magnetic resonance (MRI) imaging are emerging as a promising platform to enhance the depth of characterization in neuroscientific research. Electrically conductive, optically transparent, and MRI-compatible electrodes can optimally combine all modalities. Graphene as a suitable electrode candidate material can be grown via chemical vapor deposition (CVD) processes and sandwiched between transparent biocompatible polymers. However, due to the high graphene growth temperature (≥ 900 °C) and the presence of polymers, fabrication is commonly based on a manual transfer process of pre-grown graphene sheets, which causes reliability issues. In this paper, we present CVD-based multilayer graphene electrodes fabricated using a wafer-scale transfer-free process for use in optically transparent and MRI-compatible neural interfaces. Our fabricated electrodes feature very low impedances which are comparable to those of noble metal electrodes of the same size and geometry. They also exhibit the highest charge storage capacity (CSC) reported to date among all previously fabricated CVD graphene electrodes. Our graphene electrodes did not reveal any photo-induced artifact during 10-Hz light pulse illumination. Additionally, we show here, for the first time, that CVD graphene electrodes do not cause any image artifact in a 3T MRI scanner. These results demonstrate that multilayer graphene electrodes are excellent candidates for the next generation of neural interfaces and can substitute the standard conventional metal electrodes. Our fabricated graphene electrodes enable multimodal neural recording, electrical and optogenetic stimulation, while allowing for optical imaging, as well as, artifact-free MRI studies.