On-chip electrochemical capacitors and piezoelectric energy harvesters for self-powering sensor nodes

On-chip sensing and communications in the Internet of things platform have benefited from the miniaturization of faster and low power complementary-metal-oxide semiconductor (CMOS) microelectronics. Micro-electromechanical systems technology (MEMS) and development of novel nanomaterials have further improved the performance of sensors and transducers while also demonstrating reduction in size and power consumption. Integration of such technologies can enable miniaturized nodes to be deployed to construct wireless sensor networks for autonomous data acquisition. Their longevity, however, is determined by the lifetime of the power supply. Traditional batteries cannot fully fulfill the demands of sensor nodes that require long operational duration. Thus, we require solutions that produce their own electricity from the surroundings and store them for future utility. Furthermore, manufacturing of such a power supply must be compatible with CMOS and MEMS technology. In this thesis, we will describe on-chip electrochemical capacitors and piezoelectric energy harvesters as components of such a self-powered sensor node. Our piezoelectric microcantilevers confirm the feasibility of fabricating micro electro-mechanical-systems (MEMS) size two-degree-of-freedom systems which can address the major issue of small bandwidth of piezoelectric micro-energy harvesters. These devices use a cut-out trapezoidal cantilever beam, limited by its footprint area i.e. a 1 cm$^2$ silicon die, to enhance the stress on the cantilever\u27s free end while reducing the gap remarkably between its first two eigenfrequencies in the 400 - 500 Hz and in the 1 - 2 kHz range. The energy from the M-shaped harvesters could be stored in rGO based on-chip electrochemical capacitors. The electrochemical capacitors are manufactured through CMOS compatible, reproducible, and reliable micromachining processes such as chemical vapor deposition of carbon nanofibers (CNF) and spin coating of graphene oxide based (GO) solutions. The impact of electrode geometry and electrode thickness is studied for CNF based electrodes. Furthermore, we have also demonstrated an improvement in their electrochemical performance and yield of spin coated electrochemical capacitors through surface roughening from iron and chromium nanoparticles. The CVD grown CNF and spin coated rGO based devices are evaluated for their respective trade-offs. Finally, to improve the energy density and demonstrate the versatility of the spin coating process, we manufactured electrochemical capacitors from various GO based composites with functional groups heptadecan-9-amine and octadecanamine. The materials were used as a stack to demonstrate high energy density for spin coated electrochemical capacitors. We have also examined the possibility of integrating these devices into a power management unit to fully realize a self-powering on-chip power supply through survey of package fabrication, choice of electrolyte, and device assembly

Towards an on-chip power supply: Integration of micro energy harvesting and storage techniques for wireless sensor networks

The lifetime of a power supply in a sensor node of a wireless sensor network is the decisive factor in the longevity of the system. Traditional Li-ion batteries cannot fulfill the demands of sensor networks that require a long operational duration. Thus, we require a solution that produces its own electricity from its surrounding and stores it for future utility. Moreover, as the sensor node architecture is developed on complimentary metal-oxide-semiconductor technology (CMOS), the manufacture of the power supply must be compatible with it. In this thesis, we shall describe the components of an on-chip lifetime power supply that can harvest the vibrational mechanical energy through piezoelectric microcantilevers and store it in a reduced graphene oxide (rGO) based microsupercapacitor, and that is fabricated through CMOS compatible techniques. Our piezoelectric microcantilevers confirm the feasibility of fabricating micro electro- mechanical-systems (MEMS) size two-degree-of-freedom systems which can solve the major issue of small bandwidth of piezoelectric micro-energy harvesters. These devices use a cut-out trapezoidal cantilever beam to enhance the stress on the cantilever’s free end while reducing the gap remarkably between its first two eigenfrequencies in 400 - 500 Hz and 1 - 2 kHz range. The energy from the M-shaped harvesters will be stored in rGO based microsupercapacitors. These microsupercapacitors are manufactured through a fully CMOS compatible, reproducible, and reliable micromachining processes. Furthermore, we have also demonstrated an improvement in their electrochemical performance and yield of fabrication through surface roughening from iron nanoparticles. We have also examined the possibility of integrating these devices into a power management unit to fully realize a lifetime power supply for wireless sensor networks

Investigation of vertical carbon nanosheet growth and its potential for microsupercapacitors

One of the biggest applications that are coming with the Internet of Things (IoT) are miniaturized sensor networks that connect wirelessly to each other and the internet. Microsupercapacitors (MSCs) are ideal to power these devices, with large cyclability and lifetime. Porous carbons are the material of choice for these devices, but their morphology and manufacturing are far from optimized. Vertically oriented graphene MSCs have shown great promise due to their high specific surface areas and conductivity. In this work, the growth of vertically aligned carbon nanosheets (CNS) on 2-inch wafers has been studied, and it has been used as active material to manufacture MSC and transmission line model (TLM) wafers. The fabricated CNS MSC devices show a capacitance of 7.4 ?F (50.7 ?F/cm2, normalized to the area of the electrodes), a five-times increase from previous results obtained by the group

Comparison of Thermally Grown Carbon Nanofiber-Based and Reduced Graphene Oxide-Based CMOS-Compatible Microsupercapacitors

Microsupercapacitors as miniature energy storage devices require complementary metal-oxide-semiconductor (CMOS) compatible techniques for electrode deposition to be integrated in wireless sensor network sensor systems. Among several processing techniques, chemical vapor deposition (CVD) and spin coating, present in CMOS manufacturing facilities, are the two most viable processes for electrode growth and deposition, respectively. To make an argument for choosing either of these techniques to fabricate MSCs utilizable for an on-chip power supply, we need a comparative assessment of their electrochemical performance. Herein, the evaluation of MSCs with CVD-grown carbon nanofiber (CNF)-based and spin-coated reduced graphene oxide (rGO)-based electrodes is reported. The devices are compared for their capacitance, energy and power density, charge retention, characteristic frequencies, and ease of fabrication over a large sweep of scan rates, current densities, and frequencies. The rGO-based MSCs demonstrate 112 mu F cm(-2) at 100 mV s(-1) and a power density of 12.8 mW cm(-2). The CNF-based MSCs show 269.7 mu F cm(-2) and 30.8 mW cm(-2). CVD-grown CNF outperforms spin-coated rGO in capacitive storage at low frequencies, whereas the latter is better in terms of charge retention and high-frequency capacitance response

Finger Number and Device Performance: A Case Study of Reduced Graphene Oxide Microsupercapacitors

Microsupercapacitors (MSCs) are recognized as suitable energy storage devices for the internet of things (IoTs) applications. Herein is described the work conducted to assess the areal energy and power densities of MSCs with 2, 10, 20, and 40 interdigital finger electrodes on a fixed device footprint area (the finger interspacing is fixed at 40 μm, and the finger width and length are allowed to vary to fit the footprint area). The MSCs are based on reduced graphene oxide (rGO) materials and fabricated with a spin-coating and etch method. The performance evaluation indicates a strong dependency of areal capacitance and energy density on the number of fingers, and the maximum (impedance match) power density is also influenced to a relatively large extent, whereas the average power density is not sensitive to the configuration parameters in the present evaluation settings (scan rate 20–200 mV s−1 and current density of 100 μA cm−2). For the rGO-based devices, the equivalent distributed resistance may play an important role in determining the device resistance and power-related performance

Durable Activated Carbon Electrodes with a Green Binder

Herein, the fabrication and electrochemical performance of thick (180−280 μm) activated carbon (AC) electrodes with carbonized lignin-derived carbon fiber (LCF) inclusions are reported. Efforts are taken in fabricating robust free-standing electrodes from an environmentally friendly binder, microfibrillated cellulose (MFC), considering the biologically hazardous nature of other commonly used binders like polytetrafluoroethylene (PTFE), n-methyl-2-pyrrolidone (NMP), and polyvinylidene fluoride (PVDF). Generally, electrodes composed of MFC binder are prone to cracking upon drying, especially with higher mass loadings, which leads to nonflexibility and poor device stability. The LCF inclusions into the AC electrode with MFC binders not only increase flexibility but also contribute to better conductivity in the electrodes. The LCFs act as an intermediate layer among AC particles and serve as conductive pathways, facilitating exposure of more active surfaces to the electrolyte. A thick electrode with high mass loading of 10 mg cm−2 is achieved. The results show that by incorporating 2 wt% LCF to the AC material, the best device with 5 mg cm−2 delivers a specific capacitance of 97 F g−1, while the specific capacitance of the reference AC device without LCF is 85 F g−1

Alkyl-Amino Functionalized Reduced-Graphene-Oxide–heptadecan-9-amine-Based Spin-Coated Microsupercapacitors for On-Chip Low Power Electronics

With the miniaturization of microelectronics, integrated circuits can benefit from an on-chip solid-state power supply. Microsupercapacitors (MSCs), owing to their long lifetimes and complementary metal-oxide-semiconductor (CMOS) compatible fabrication, can be a potential on-chip energy storage unit. MSCs fabricated through spin coating graphene-oxide (GrO) often suffer from insufficient electrode thicknesses that lead to low energy densities. It, therefore, requires functionalizations for GrO that can improve the MSC electrode thickness and, thereby, the performance of the MSC. Thus, herein, the MSCs fabricated of alkyl-amino functionalized reduced-graphene-oxide–heptadecan-9-amine (rGO) are reported for enhanced electrode thickness, high capacitance, and lower series resistance compared with functionalized GrO-based MSCs (GO-MSCs). The functionalized rGO solves a significant issue of inadequate electrode thickness in wafer-scale MSC fabrication while achieving higher energy densities in fewer spin coatings. The rGO-MSC displays an areal capacitance of 108 μF cm−2\ua0compared with 24 μF cm−2\ua0for the GO-MSC while also demonstrating more than twice its power density in an integration compatible ionic liquid electrolyte 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfony)imide (EMIM-TFSI)

Investigation of palladium current collectors for vertical graphene-based microsupercapacitors

As microsystems are reduced in size and become integrated in the Internet of Things (IoT), they require an adequate power supply which can be integrated at the same size scale. Microsupercapacitors (MSCs), if coupled with on-chip harvesters, can offer solutions for a self-sustaining, on-chip power supply. However, the implementation of reliable MSC wafer-scale production compatible with CMOS technology remains a challenge. Palladium (Pd) is known as a CMOS compatible metal and, in this paper, we investigate the use of Pd as a contact material for vertical graphene (VG) electrodes in wafer-scale MSC fabrication. We show that a Ti diffusion barrier is required to prevent short-circuiting for the successful employment of Pd contacts. The fabricated MSCs demonstrate a capacitance of 1.3 μF/cm2 with an energy density of 0.42 μJ/cm2. Thus, utilization of a Ti diffusion barrier with a CMOS compatible Pd metal electrode is a step towards integrating MSCs in semiconductor microsystems

Impact of electrode geometry and thickness on planar on-chip microsupercapacitors

We report an assessment of the influence of both finger geometry and vertically-oriented carbon nanofiber lengths in planar micro-supercapacitors. Increasing the finger number leads to an up-scaling in areal power densities, which increases with scan rate. Growing the nanofibers longer, however, does not lead to a proportional growth in capacitance, proposedly related to limited ion penetration of the electrode

Enhanced Electrode Deposition for On-Chip Integrated Micro-Supercapacitors by Controlled Surface Roughening

On-chip micro-supercapacitors (MSCs), integrated with energy harvesters, hold substantial promise for developing self-powered wireless sensor systems. However, MSCs have conventionally been manufactured through techniques incompatible with semiconductor fabrication technology, the most significant bottleneck being the electrode deposition technique. Utilization of spin-coating for electrode deposition has shown potential to deliver several complementary metal-oxide-semiconductor (CMOS)-compatible MSCs on a silicon substrate. Yet, their limited electrochemical performance and yield over the substrate have remained challenges obstructing their subsequent integration. We report a facile surface roughening technique for improving the wafer yield and the electrochemical performance of CMOS-compatible MSCs, specifically for reduced graphene oxide as an electrode material. A 4 nm iron layer is deposited and annealed on the wafer substrate to increase the roughness of the surface. In comparison to standard nonroughened MSCs, the increase in surface roughness leads to a 78% increased electrode thickness, 21% improvement in mass retention, 57% improvement in the uniformity of the spin-coated electrodes, and a high yield of 87% working devices on a 2″ silicon substrate. Furthermore, these improvements directly translate to higher capacitive performance with enhanced rate capability, energy, and power density. This technique brings us one step closer to fully integrable CMOS-compatible MSCs in self-powered systems for on-chip wireless sensor electronics. \ua