A. De Luca

Bio: A. De Luca is an academic researcher from University of Cambridge. The author has contributed to research in topics: Deep reactive-ion etching & Thermopile. The author has an hindex of 11, co-authored 23 publications receiving 428 citations.

CMOS integration of inkjet-printed graphene for humidity sensing.

Abstract: We report on the integration of inkjet-printed graphene with a CMOS micro-electro-mechanical-system (MEMS) microhotplate for humidity sensing. The graphene ink is produced via ultrasonic assisted liquid phase exfoliation in isopropyl alcohol (IPA) using polyvinyl pyrrolidone (PVP) polymer as the stabilizer. We formulate inks with different graphene concentrations, which are then deposited through inkjet printing over predefined interdigitated gold electrodes on a CMOS microhotplate. The graphene flakes form a percolating network to render the resultant graphene-PVP thin film conductive, which varies in presence of humidity due to swelling of the hygroscopic PVP host. When the sensors are exposed to relative humidity ranging from 10–80%, we observe significant changes in resistance with increasing sensitivity from the amount of graphene in the inks. Our sensors show excellent repeatability and stability, over a period of several weeks. The location specific deposition of functional graphene ink onto a low cost CMOS platform has the potential for high volume, economic manufacturing and application as a new generation of miniature, low power humidity sensors for the internet of things.

Temperature-modulated graphene oxide resistive humidity sensor for indoor air quality monitoring

Abstract: In this paper we present a temperature-modulated graphene oxide (GO) resistive humidity sensor that employs complementary-metal-oxide-semiconductor (CMOS) micro-electro-mechanical-system (MEMS) micro-hotplate technology for the monitoring and control of indoor air quality (IAQ). GO powder is obtained by chemical exfoliation, dispersed in water and deposited via ink-jet printing onto a low power micro-hotplate. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) show the typical layered and wrinkled morphology of the GO. Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and Fourier transform infra-red (FTIR) spectroscopy indicate that the GO flakes possess a significant number of oxygen containing functional groups (epoxy, carbonyl, hydroxyl) extremely attractive for humidity detection. Electro-thermal characterisation of the micro-hotplates shows a thermal efficiency of 0.11 mW per °C, resulting in a sensor DC power consumption of only 2.75 mW at 50 °C. When operated in an isothermal mode, the sensor response is detrimentally affected by significant drift, hysteretic behaviour, slow response/recovery times and hence poor RH level discrimination. Conversely, a temperature modulation technique coupled with a differential readout methodology results in a significant reduction of the sensor drift, improved linear response with a sensitivity of 0.14 mV per %, resolution below 5%, and a maximum hysteresis of ±5%; response and recovery times equal to 189 ± 49 s and 89 ± 5 s, respectively. These performance parameters satisfy current IAQ monitoring requirements. We have thus demonstrated the effectiveness of integrating GO on a micro-hotplate CMOS-compatible platform enabling temperature modulation schemes to be easily applied in order to achieve compact, low power, low cost humidity IAQ monitoring.

Dip pen nanolithography-deposited zinc oxide nanorods on a CMOS MEMS platform for ethanol sensing

Abstract: This paper reports on the novel deposition of zinc oxide (ZnO) nanorods using a dip pen nanolithographic (DPN) technique on SOI (silicon on insulator) CMOS MEMS (micro electro mechanical system) micro-hotplates (MHP) and their characterisation as a low-cost, low-power ethanol sensor. The ZnO nanorods were synthesized hydrothermally and deposited on the MHP that comprise a tungsten micro-heater embedded in a dielectric membrane with gold interdigitated electrodes (IDEs) on top of an oxide passivation layer. The micro-heater and IDEs were used to heat up the sensing layer and measure its resistance, respectively. The sensor device is extremely power efficient because of the thin SOI membrane. The electro-thermal efficiency of the MHP was found to be 8.2 °C mW−1, which results in only 42.7 mW power at an operating temperature of 350 °C. The CMOS MHP devices with ZnO nanorods were exposed to PPM levels of ethanol in humid air. The sensitivity achieved from the sensor was found to be 5.8% ppm−1 to 0.39% ppm−1 for the ethanol concentration range 25–1000 ppm. The ZnO nanorods showed an optimum response at 350 °C. The CMOS sensor was found to have a humidity dependence that needs consideration in real-world application. The sensors were also found to be selective towards ethanol when tested in the presence of toluene and acetone. We believe that the integration of ZnO nanorods using DPN lithography with a CMOS MEMS substrate offers a low cost, low power, smart ethanol sensor that could be exploited in consumer electronics.

Mask-less deposition of Au-SnO2 nanocomposites on CMOS MEMS platform for ethanol detection.

Abstract: Here we report on the mask-less deposition of Au-SnO2 nanocomposites with a silicon-on-insulator (SOI) complementary metal oxide semiconductor (CMOS) micro electro mechanical system (MEMS) platform through the use of dip pen nanolithography (DPN) to create a low-cost ethanol sensor. MEMS technology is used in order to achieve low power consumption, by the employment of a membrane structure formed using deep reactive ion etching technique. The device consists of an embedded tungsten micro-heater with gold interdigitated electrodes on top of the SOI membrane. The tungsten micro-heater is used to raise the membrane temperature up to its operating temperature and the electrodes are used to measure the resistance of the nanocomposite sensing layer. The CMOS MEMS devices have high electro-thermal efficiency, with 8.2 °C temperature increase per mW power of consumption. The sensing material (Au-SnO2 nanocomposite) was synthesised starting from SnO nanoplates, then Au nanoparticles were attached chemically to the surface of SnO nanoplates, finally the mixture was heated at 700 °C in an oven in air for 4 h. This composite material was sonicated for 2 h in terpineol to make a viscous homogeneous slurry and then 'written' directly across the electrode area using the DPN technique without any mask. The devices were characterised by exposure to ethanol vapour in humid air in the concentration range of 100-1000 ppm. The sensitivity varied from 1.2 to 0.27 ppm(-1) for 100-1000 ppm of ethanol at 10% relative humid air. Selectivity measurements showed that the sensors were selective towards ethanol when they were exposed to acetone and toluene.

Experimental, analytical and numerical investigation of non-linearity of SOI diode temperature sensors at extreme temperatures

Abstract: This paper presents the performance of a silicon-on-insulator (SOI) p+/p-well/n+ diode temperature sensor, which can operate in an extremely wide temperature range of 80 K to 1050 K. The thermodiode is placed underneath a tungsten micro-heater which is embedded in a thin dielectric membrane, obtained with a post-CMOS deep reactive ion etching process. Analytical and numerical models are used to support experimental findings. Non-linearity, sensitivity and methods for their reduction and enhancement, respectively, are investigated in detail.

2D-Crystal-Based Functional Inks

Abstract: The possibility to produce and process graphene, related 2D crystals, and heterostructures in the liquid phase makes them promising materials for an ever-growing class of applications as composite materials, sensors, in flexible optoelectronics, and energy storage and conversion. In particular, the ability to formulate functional inks with on-demand rheological and morphological properties, i.e., lateral size and thickness of the dispersed 2D crystals, is a step forward toward the development of industrial-scale, reliable, inexpensive printing/coating processes, a boost for the full exploitation of such nanomaterials. Here, the exfoliation strategies of graphite and other layered crystals are reviewed, along with the advances in the sorting of lateral size and thickness of the exfoliated sheets together with the formulation of functional inks and the current development of printing/coating processes of interest for the realization of 2D-crystal-based devices.

Functional inks and printing of two-dimensional materials.

Abstract: Graphene and related two-dimensional materials provide an ideal platform for next generation disruptive technologies and applications. Exploiting these solution-processed two-dimensional materials in printing can accelerate this development by allowing additive patterning on both rigid and conformable substrates for flexible device design and large-scale, high-speed, cost-effective manufacturing. In this review, we summarise the current progress on ink formulation of two-dimensional materials and the printable applications enabled by them. We also present our perspectives on their research and technological future prospects.

Production and processing of graphene and related materials

Abstract: © 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown.

Black phosphorus ink formulation for inkjet printing of optoelectronics and photonics

Abstract: Black phosphorus is a two-dimensional material of great interest, in part because of its high carrier mobility and thickness dependent direct bandgap. However, its instability under ambient conditions limits material deposition options for device fabrication. Here we show a black phosphorus ink that can be reliably inkjet printed, enabling scalable development of optoelectronic and photonic devices. Our binder-free ink suppresses coffee ring formation through induced recirculating Marangoni flow, and supports excellent consistency ( 30 days) oxidation. We demonstrate printed black phosphorus as a passive switch for ultrafast lasers, stable against intense irradiation, and as a visible to near-infrared photodetector with high responsivities. Our work highlights the promise of this material as a functional ink platform for printed devices. Atomically thin black phosphorus shows promise for optoelectronics and photonics, yet its instability under environmental conditions and the lack of well-established large-area synthesis protocols hinder its applications. Here, the authors demonstrate a stable black phosphorus ink suitable for printed ultrafast lasers and photodetectors.

Reduced graphene oxide today

Abstract: Reduced graphene oxide has similar mechanical, optoelectronic or conductive properties to pristine graphene because it possesses a heterogeneous structure comprised of a graphene-like basal plane that is additionally decorated with structural defects and populated with areas containing oxidized chemical groups. The graphene-like properties make reduced graphene oxide a highly desirable material to be used in a plethora of sensorial, biological, environmental or catalytic applications as well as optoelectronic and storage devices. To further advance the development of the existent technologies and to design novel and better applications based on reduced graphene oxide, it is first necessary to understand which synthetic routes and processing strategies are suitable to significantly boost specific properties of this material alone or as a component in various composites. Therefore, in this work, we review the most important categories of recent applications based on reduced graphene oxide, with the emphasis on the relationship between the enhanced composite/device functionality and methods used to synthesize, to functionalize and/or to process and to structure reduced graphene oxide.