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Progress in Nanoporous Templates: Beyond Anodic Aluminum Oxide and Towards Functional Complex Materials
Successful synthesis of ordered porous, multi-component complex materials requires a series of coordinated processes, typically including fabrication of a master template, deposition of materials within the pores to form a negative structure, and a third deposition or etching process to create the final, functional template. Translating the utility and the simplicity of the ordered nanoporous geometry of binary oxide templates to those comprising complex functional oxides used in energy, electronic, and biology applications has been met with numerous critical challenges. This review surveys the current state of commonly used complex material nanoporous template synthesis techniques derived from the base anodic aluminum oxide (AAO) geometry
Investigation of nanoporous Thin-film Alumina Templates
This paper presents the results of a systematic study of the fabrication of thin-film alumina templates on silicon and other substrates. Such templates are of significant interest for the low-cost implementation of semiconductor and metal nanostructure arrays. In addition, thin-film alumina templates on silicon have the potential for nanostructure integration with silicon electronics. Formation of thin-film alumina templates on silicon substrates was investigated under different fabrication conditions, and the dependence of pore morphology and pore formation rate on process parameters was evaluated. In addition, process conditions for improved pore size distribution and periodicity were determined. The template/silicon interface, important for nanostructure integration on silicon, was investigated using capacitance-voltage measurements and electron microscopy, and was found to be of good device quality. Formation of thin-film alumina templates on nonsilicon substrates such as glass, indium-tin-oxide-coated glass, and silicon carbide was also investigated
Single and Multi-dimensional AAO Template Synthesized Heterogeneous Nanostructures for Electrochemical Energy Storage
Anodic aluminum oxide (AAO) has been successfully used to fabricate a variety of well-ordered, regular nanostructured systems for a range of applications including electrochemical energy storage technologies. Template synthesized nanomaterials based on AAO can lead to well-designed nanoarchitectures composed of multiple favorable (high energy capacity, high electrical conductivity, strong mechanical strength) electrical energy storage materials and also one and three dimensional. Combining nanomaterials within a single system to form heterogeneous nanostructures leads to synergic effects unrealized with single components. Adding dimensionality to nanostructures potentially offers drastic improvements in both energy density and power density.
This dissertation describes the design, fabrication, and characterization of heterogeneous nanostructures based on AAO template synthesis methods for use as supercapacitor electrodes. The first approach utilizes two straightforward deposition techniques, atomic layer deposition and electrochemical deposition, for the construction of MnO2/TiN nanotube arrays. Both the inner and outer surfaces of the nanotubes, where the charge storage takes place, are exploited for enhanced capacitance. The second approach uses a novel well-ordered three-dimensional nanostructured template based on the modification of AAO during pore formation. A network of interconnecting pores is produced and demonstrates the controllable nature of AAO pore growth. An additional AAO modification to the pore barrier layer allows for electrical contact to the bottom aluminum substrate. The potential for new nanoarchitectures using the electrochemically modified AAO template, especially in multiple dimensions, is further realized using atomic layer deposition and chemical synthesis techniques
NANOPOROUS AAO: A PLATFORM FOR REGULAR HETEROGENEOUS NANOSTRUCTURES AND ENERGY STORAGE DEVICES
Nanoporous anodic aluminum oxide (AAO) has vast implications as a tool for nanoscience research and as a nanostructure in which nanoscale devices can be fabricated because of its regular and ordered nanopores. Self-assembly plays a critical role in pore ordering, causing nanopores to grow parallel with one another in high density. The mild electrochemical conditions in which porous AAO grows along with its relatively cheap starting materials makes this nanomaterial a cost effective alternative to advanced photolithography techniques for forming high surface area nanostructures over large areas.
In this research, atomic layer deposition (ALD) was used to deposit conformal films within in nanoporous AAO with hopes to 1) develop methodologies to characterize ALD depositions within its high aspect ratio nanopores and 2) to better understand how to use nanoporous AAO templates as a scaffold for energy devices, specifically Metal-Insulator-Metal (MIM) capacitors. Using the nanotube template synthesis method, ALD films were deposited onto nanoporous AAO, later removing the films deposited within the templates nanopores for characterization in TEM. This nanotube metrology characterization involves first obtaining images of full length ALD-AAO nanotubes, and then measuring wall thickness as a function of depth within the nanopore. MIM nanocapacitors were also constructed in vertical AAO nanopores by deposition of multilayer ALD films. MIM stacks were patterned into micro-scale capacitors for electrical characterization
Development of capacitive-type sensors by electrochemical anodization: humidity and touch sensing applications
This work describes the development of a capacitive-type sensor created from nanoporous anodic aluminium oxide (NP-AAO) prepared by the one-step anodization method conducted in potentiostatic mode and performed in a low-cost homemade system. A series of samples were prepared via an anodization campaign carried out on different acid electrolytes, in which the anodization parameters were adjusted to investigate the effect of pore size and porosity on the capacitive sensing performance. Two sensor test cases are investigated. The first case explores the use of highly uniform NP-AAO structures for humidity sensing applications while the second analyses the use of NP-AAO as a capacitive touch sensor for biological applications, namely, to detect the presence of small objects such as bacterial colonies of Escherichia Coli. A mathematical model based on equivalent electrical circuits was developed to evaluate the effect of humidity condensation (inside the pores) on the sensor capacitance and also to estimate the capacitance change of the sensor due to pore blocking by the presence of a certain number of bacterial microorganisms. Regarding the humidity sensing test cases, it was found that the sensitivity of the sensor fabricated in a phosphoric acid solution reaches up to 39 (pF/RH%), which is almost three times higher than the sensor fabricated in oxalic acid and about eight times higher than the sensor fabricated in sulfuric acid. Its improved sensitivity is explained in terms of the pore size effect on the mean free path and the loss of Brownian energy of the water vapour molecules. Concerning the touch sensing test case, it is demonstrated that the NP-AAO structures can be used as capacitive touch sensors because the magnitude of the capacitance change directly depends on the number of bacteria that cover the nanopores; the fraction of the electrode area activated by bacterial pore blocking is about 4.4% and 30.2% for B1 (E. Coli OD600nm=0.1) and B2 (E. Coli OD600nm=1) sensors, respectively.This research was funded by: the Portuguese Foundation for Science and Technology (FCT) under the strategic funding grants UIDB/04029/2020, UIDB/04650/2020 and UIDB/04469/20 units; and, the European Regional Development Fund under the scope of Norte2020 program grant NORTE-01-0145-FEDER-000004, BioTecNorte.info:eu-repo/semantics/publishedVersio
Development of capacitive-type sensors by electrochemical anodization: Humidity and touch sensing applications
This work describes the development of a capacitive-type sensor created from nanoporous anodic aluminium oxide (NP-AAO) prepared by the one-step anodization method conducted in potentiostatic mode and performed in a low-cost homemade system. A series of samples were prepared via an anodization campaign carried out on different acid electrolytes, in which the anodization parameters were adjusted to investigate the effect of pore size and porosity on the capacitive sensing performance. Two sensor test cases are investigated. The first case explores the use of highly uniform NP-AAO structures for humidity sensing applications while the second analyses the use of NP-AAO as a capacitive touch sensor for biological applications, namely, to detect the presence of small "objects " such as bacterial colonies of Escherichia Coli. A mathematical model based on equivalent electrical circuits was developed to evaluate the effect of humidity condensation (inside the pores) on the sensor capacitance and also to estimate the capacitance change of the sensor due to pore blocking by the presence of a certain number of bacterial microorganisms. Regarding the humidity sensing test cases, it was found that the sensitivity of the sensor fabricated in a phosphoric acid solution reaches up to 39 (pF/RH%), which is almost three times higher than the sensor fabricated in oxalic acid and about eight times higher than the sensor fabricated in sulfuric acid. Its improved sensitivity is explained in terms of the pore size effect on the mean free path and the loss of Brownian energy of the water vapour molecules. Concerning the touch sensing test case, it is demonstrated that the NP-AAO structures can be used as capacitive touch sensors because the magnitude of the capacitance change directly depends on the number of bacteria that cover the nanopores; the fraction of the electrode area activated by bacterial pore blocking is about 4.4% and 30.2% for B1 (E. Coli OD600nm = 0.1) and B2 (E. Coli OD600nm = 1) sensors, respectively.This research was funded by: the Portuguese Foundation for Science and Technology (FCT) under the strategic funding grants UIDB/04029/2020, UIDB/04650/2020 and UIDB/04469/2020 units; and, the European Regional Development Fund under the scope of Norte2020 program grant NORTE-01-0145-FEDER-000004, BioTecNorte
Recent progress of fabrication, characterization, and applications of anodic aluminum oxide (AAO) membrane: A review
The progress of membrane technology with the development of membranes with
controlled parameters led to porous membranes. These membranes can be formed
using different methods and have numerous applications in science and
technology. Anodization of aluminum in this aspect is an electro-synthetic
process that changes the surface of the metal through oxidation to deliver an
anodic oxide layer. This process results in a self-coordinated, exceptional
cluster of round and hollow formed pores with controllable pore widths,
periodicity, and thickness. After the initial introduction, the paper proceeds
with a brief overview of anodizing process. That engages anodic aluminum oxide
(AAO) layers to be used as formats in various nanotechnology applications
without the necessity for expensive lithographical systems. This review article
surveys the current status of the investigation on AAO membranes. A
comprehensive analysis is performed on AAO membranes in applications;
filtration, sensors, drug delivery, template-assisted growth of various
nanostructures. Their multiple usages in nanotechnology have also been
discussed to gather nanomaterials and devices or unite them into specific
applications, such as nano-electronic gadgets, channel layers, and clinical
platforms tissue designing. From this review, the fact that the specified
enhancement of properties of AAO can be done by varying geometric parameters of
AAO has been highlighted. No review paper focused on a detailed discussion of
applications of AAO with prospects and challenges. This review paper represents
the formation, properties, applications with objective consideration of the
prospects and challenges of AAO applications. The prospects may appeal to
researchers to promote the development of unique membranes with
functionalization and controlled geometric parameters and check the feasibility
of the AAO membranes in nano-devices.Comment: 36 pages, 19 figures, 8 table
Applications of Biogenic Silica Nanostructures from Diatoms
abstract: Biogenic silica nanostructures, derived from diatoms, possess highly ordered porous hierarchical nanostructures and afford flexibility in design in large part due to the availability of a great variety of shapes, sizes, and symmetries. These advantages have been exploited for study of transport phenomena of ions and molecules towards the goal of developing ultrasensitive and selective filters and biosensors. Diatom frustules give researchers many inspiration and ideas for the design and production of novel nanostructured materials. In this doctoral research will focus on the following three aspects of biogenic silica: 1) Using diatom frustule as protein sensor. 2) Using diatom nanostructures as template to fabricate nano metal materials. 3) Using diatom nanostructures to fabricate hybrid platform.
Nanoscale confinement biogenetic silica template-based electrical biosensor assay offers the user the ability to detect and quantify the biomolecules. Diatoms have been demonstrated as part of a sensor. The sensor works on the principle of electrochemical impedance spectroscopy. When specific protein biomarkers from a test sample bind to corresponding antibodies conjugated to the surface of the gold surface at the base of each nanowell, a perturbation of electrical double layer occurs resulting in a change in the impedance.
Diatoms are also a new source of inspiration for the design and fabrication of nanostructured materials. Template-directed deposition within cylindrical nanopores of a porous membrane represents an attractive and reproducible approach for preparing metal nanopatterns or nanorods of a variety of aspect ratios. The nanopatterns fabricated from diatom have the potential of the metal-enhanced fluorescence to detect dye-conjugated molecules.
Another approach presents a platform integrating biogenic silica nanostructures with micromachined silicon substrates in a micro/nano hybrid device. In this study, one can take advantages of the unique properties of a marine diatom that exhibits nanopores on the order of 40 nm in diameter and a hierarchical structure. This device can be used to several applications, such as nano particles separation and detection. This platform is also a good substrate to study cell growth that one can observe the reaction of cell growing on the nanostructure of frustule.Dissertation/ThesisDoctoral Dissertation Materials Science and Engineering 201
Nanowire Zinc Oxide MOSFET Pressure Sensor
Fabrication and characterization of a new kind of pressure sensor using self-assembly Zinc Oxide (ZnO) nanowires on top of the gate of a Metal-Oxide-Semiconductor Field-Effect Transistor (MOSFET) is presented. Self-assembly ZnO nanowires were fabricated with a diameter of 80 nm and 800 nm height (80:8 aspect ratio) on top of the gate of the MOSFET. The sensor showed a 110% response in the drain current due to pressure, even with the expected piezoresistive response of the silicon device removed from the measurement. The pressure sensor was fabricated through low temperature bottom up ultrahigh aspect ratio ZnO nanowire growth using anodic alumina oxide (AAO) templates. The pressure sensor has two main components: MOSFET and ZnO nanowires. Silicon Dioxide growth, photolithography, dopant diffusion, and aluminum metallization were used to fabricate a basic MOSFET. In the other hand, a combination of aluminum anodization, alumina barrier layer removal, ZnO atomic layer deposition (ALD), and wet etching for nanowire release were optimized to fabricate the sensor on a silicon wafer. The ZnO nanowire fabrication sequence presented is at low temperature making it compatible with CMOS technology
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