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Synthesis, Characterization and Applications of Metal Oxide Nanostructures
Linköping University, Department of Science and Technology. Linköping University, The Institute of Technology.
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The main objective of nanotechnology is to build self-powered nanosystems that are ultrasmall in size, exhibit super sensitivity, extraordinary multi functionality, and extremely low power consumption. As we all know that 21st century has brought two most important challenges for us. One is energy shortage and the other is global warming. Now to overcome these challenges, it is highly desirable to develop nanotechnology that harvests energy from the environment to fabricate self-power and low-carbon nanodevices. Therefore a self-power nanosystem that harvests its operating energy from the environment is an attractive proposition. This is also feasible for nanodevices owing to their extremely low power consumption. One advantageous approach towards harvesting energy from the environment is the utilization of semiconducting piezoelectric materials, which facilitate the conversion of mechanical energy into electrical energy. Among many piezoelectric materials ZnO has the rare attribute of possessing both piezoelectric and semiconducting properties. But most applications of ZnO utilize either the semiconducting or piezoelectric property, and now it’s time to fully employ the coupled semiconducting-piezoelectric properties to form  the basis for electromechanically coupled nanodevices. Since wurtzite zinc oxide (ZnO) is structurally noncentral symmetric and has the highest piezoelectric tensor among tetrahedrally bonded semiconductors, therefore it becomes a promising candidate for energy harvesting applications. ZnO is relatively biosafe and biocompatible as well, so it can be used at large scale without any harm to the living environment.

The synthesis of another transition metal oxide known as Co3O4 is also important due to its potential usage in the material science, physics and chemistry fields. Co3O4 has been studied extensively due to low cost, low toxicity, the most naturally abundant, high surface area, good redox, easily tunable surface and structural properties. These significant properties enable Co3O4 fruitful for developing variety of nanodevices. Co3O4 nanostructures have been focused considerably in the past decade due to their high electro-chemical performance, which is essential for developing highly sensitive sensor devices.

I started my work with the synthesis of ZnO nanostructures with a focus to improve the amount of harvested energy by utilizing oxygen plasma treatment. Then I grow ZnO nanorods on different flexible substrates, in order to observe the effect of substrate on the amount of harvested energy. After that I worked on understanding the mechanism and causes of variation in the resulting output potential generated from ZnO nanorods. My next target belongs to an innovative approach in which AFM tip decorated with ZnO nanorods was utilized to improve the output energy. Then I investigated Co3O4 nanostructures though the effect of anions and utilized one of the nanostructure to develop a fast and reliable pH sensor. Finally to take the advantage of higher degree of redox chemistry of NiCo0O4 compared to the single phase of nickel oxide and cobalt oxide, a sensitive glucose sensor is developed by immobilizing glucose oxidase.

However, there were problems with the mechanical robustness, lifetime, output stability and environmental adaptability of such devices, therefore more work is going on to find out new ways and means in order to improve the performance of fabricated nanogenerators and sensors.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2014. , 71 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1610
Keyword [en]
Aqueous chemical growth method, ZnO nanorods, Oxygen plasma treatment, Piezoelectric and mechanical properties, Atomic force microscope, Nanoindentation, Co3O4 nanostructures, Anions effect, pH sensor, NiCo2O4 nanostructures, Glucose sensor
National Category
Physical Sciences Nano Technology
Identifiers
URN: urn:nbn:se:liu:diva-108894DOI: 10.3384/diss.diva-108894ISBN: 978-91-7519-265-9 (print)OAI: oai:DiVA.org:liu-108894DiVA: diva2:733762
Public defence
2014-08-22, K 3, Kåkenhus, Campus Norrköping, Linköpings universitet, Linköping, 10:00 (English)
Opponent
Supervisors
Available from: 2014-07-11 Created: 2014-07-11 Last updated: 2014-08-18Bibliographically approved
List of papers
1. The improved piezoelectric properties of ZnO nanorods with oxygen plasma treatment on the single layer graphene coated polymer substrate
Open this publication in new window or tab >>The improved piezoelectric properties of ZnO nanorods with oxygen plasma treatment on the single layer graphene coated polymer substrate
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2014 (English)In: Physica Status Solidi (a) applications and materials science, ISSN 1862-6300, E-ISSN 1862-6319, Vol. 211, no 2, 455-459 p.Article in journal (Refereed) Published
Abstract [en]

The step towards the fabrication of nanodevices with improved performance is of high demand; therefore, in this study, oxygen plasma treated ZnO nanorods based piezoelectric nanogenerator is developed on the single layer graphene coated PET flexible polymer substrate. ZnO nanorods on the single layer graphene are grown by hydrothermal growth method and the structural study is carried out by using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The piezoelectric properties of ZnO nanorods with and without plasma treatment were investigated by atomic force microscopy (AFM). The oxygen plasma treated sample of ZnO nanorods showed significant increase in the piezoelectric potential which could be due to the decrease in the defects levels in the ZnO and also increase in the mechanical properties of ZnO nanorods. Furthermore X-ray photoelectron spectroscopy (XPS) confirms that the filling of vacancies by oxygen in the matrix of ZnO using oxygen plasma treatment has gave an enhanced piezoelectric potential compared to the sample of ZnO nanorods not treated with oxygen plasma. In addition to XPS experiment, cathodoluminescence (CL) technique was used for the determination of defect level in the ZnO nanorods after the treatment of oxygen plasma and the obtained information supported the XPS data of oxygen plasma treatment sample by showing the decreased level of defect levels in the prepared sample. From the XPS and CL studies, it is observed that the defect level has significant influence on the piezoelectric potential of the ZnO nanostructures.

Place, publisher, year, edition, pages
Wiley-VCH Verlag, 2014
Keyword
piezoelectric nanogenerator; plasma treatment; single layer graphene; zinc oxide
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-105762 (URN)10.1002/pssa.201300330 (DOI)000332000500030 ()
Available from: 2014-04-07 Created: 2014-04-04 Last updated: 2017-12-05
2. The effect of oxygen-plasma treatment on the mechanical andpiezoelectrical properties of ZnO nanorods
Open this publication in new window or tab >>The effect of oxygen-plasma treatment on the mechanical andpiezoelectrical properties of ZnO nanorods
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2014 (English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 608, 235-238 p.Article in journal (Refereed) Published
Abstract [en]

We have studied the effect of oxygen plasma treatment on piezoelectric response and on the mechanical stability of ZnO nanorods synthesized on FTO by using ACG method. XRD and SEM techniques have shown highly dense and uniformly distributed nanorods. The piezoelectric properties and mechanical stability of as-grown and oxygen plasma treated samples were investigated by using nanoindentation technique. The comparison of load–displacement curves showed that the oxygen plasma treated samples are much stiffer and show higher generated piezo-voltage. This study demonstrates that the oxygenplasma treatment is a good option to fabricate reliable and efficient nanodevices for enhanced generation of piezoelectricity.

Place, publisher, year, edition, pages
Elsevier, 2014
National Category
Materials Engineering
Identifiers
urn:nbn:se:liu:diva-108547 (URN)10.1016/j.cplett.2014.06.018 (DOI)000340202600042 ()
Available from: 2014-06-30 Created: 2014-06-30 Last updated: 2017-12-05
3. Comparative Study of Energy Harvesting from ZnO Nanorods Using Different Flexible Substrates
Open this publication in new window or tab >>Comparative Study of Energy Harvesting from ZnO Nanorods Using Different Flexible Substrates
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2014 (English)In: Energy Harvesting and Systems, ISSN 2329-8774, Vol. 1, no 1-2, 19-26 p.Article in journal (Refereed) Published
Abstract [en]

The step toward the fabrication of nanodevices with low cost and improved performance is of high demand; therefore, in the present study, different flexible substrates like common paper, textile fabric, plastic and aluminum foil have been utilized to harvest electrical energy. ZnO nanorods (NRs) were grown by using lowtemperature aqueous chemical growth method. The obtained ZnO NRs were highly dense, well aligned, uniformly distributed over the substrates and exhibited good crystal quality. The structural study was carried out by using X-ray powder diffraction and scanning electron microscopy. The piezoelectric properties of ZnO NRs were investigated by the help of an atomic force microscope using contact mode. The measurements of generated piezoelectricity were around 16.2 mV, 23.2 mV, 38.5 mV and 43.3 mV for common paper, textile fabric, plastic and aluminum foil, respectively. This investigation is an important step in order to study the effect of different substrates influencing the magnitude of the output voltage under identical growth and measurement conditions. We expect that this study will help identify the most suitable flexible substrate for harvesting energy. It also offers a promising alternative powering source for the next generation nanodevices using non-conventional substrates like aluminum foil. Moreover, the use of aluminum foil as flexible and low cost substrate may pave the way to develop devices in different fields including energy harvesting.

Place, publisher, year, edition, pages
Walter de Gruyter, 2014
Keyword
ZnO nanorods, flexible substrates, aqueous chemical growth, atomic force microscope
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-108226 (URN)10.1515/ehs-2013-0025 (DOI)
Available from: 2014-06-26 Created: 2014-06-26 Last updated: 2014-10-27Bibliographically approved
4. Use of ZnO nanorods grown AFM tip in the architecture of piezoelectric nanogenerator
Open this publication in new window or tab >>Use of ZnO nanorods grown AFM tip in the architecture of piezoelectric nanogenerator
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2014 (English)In: Micro & Nano Letters, ISSN 1750-0443, E-ISSN 1750-0443, Vol. 9, no 8, 539-543 p.Article in journal (Refereed) Published
Abstract [en]

The piezoelectric potential output has been studied using a ZnO nanorods (NRs) grown atomic force microscope (AFM) tip in lieu of the normally used AFM tip. The ZnO NRs were synthesised on the AFM tip and on the fluorine-doped tin oxide (FTO) glass substrate using the aqueous chemical growth method. The as-grown ZnO NRs were highly dense, well aligned and uniform both on the tip and on the substrate. The structural study was performed using X-ray diffraction and scanning electron microscopy techniques. The piezoelectric properties of as-grown ZnO NRs were investigated using an AFM in contact mode. In comparison to the AFM tip without ZnO NRs, extra positive voltage peaks were observed when the AFM tip with ZnO NRs was used. The pair of ZnO NRs on the AFM tip and on the FTO glass substrate together worked as two oppositely gliding walls (composed of ZnO NRs) and showed an enhancement in the amount of the harvested energy as much as eight times. This approach demonstrates that the use of the AFM tip with ZnO NRs is not only a good alternative to improve the design of nanogenerators to obtain an enhanced amount of harvested energy but is also simple, reliable and cost-effective.

National Category
Physical Sciences Chemical Sciences
Identifiers
urn:nbn:se:liu:diva-108893 (URN)10.1049/mnl.2014.0237 (DOI)000341502400012 ()
Available from: 2014-07-11 Created: 2014-07-11 Last updated: 2017-12-05Bibliographically approved
5. Effect of anions on the morphology of Co3O4 nanostructures grown by hydrothermal method and their pH sensing application
Open this publication in new window or tab >>Effect of anions on the morphology of Co3O4 nanostructures grown by hydrothermal method and their pH sensing application
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2014 (English)In: Journal of Electroanalytical Chemistry, ISSN 1572-6657, Vol. 717-718, 78-82 p.Article in journal (Refereed) Published
Abstract [en]

A fast, reliable, accurate, precise and sensitive pH sensor device is highly demanding for the monitoring of pH in biological, clinical and food industry samples. In this research work, the effect of anions on the morphology of cobalt oxide (Co3O4) nanostructures is investigated using low temperature chemical approach for the growth. Different anions have shown visible effect on the morphology of Co3O4 nanostructures. Scanning electron microscopy, X-ray diffraction and transmission electron microscopy techniques were used for the material characterization. This study has shown highly dense, uniform and good crystal quality of fabricated Co3O4 nanostructures. The nanostructures obtained from the cobalt chloride were used for the development of potentiometric pH sensor electrode. The pH sensor electrode showed excellent linearity and close to Nernstian response for the pH range of 3-13 with a sensitivity of -58.45 mV/pH. Moreover, the proposed sensor showed a fast response time of 53 s, and acceptable reducibility and repeatability. The highly sensitive and a fast time response of the proposed sensor device indicate its potential application for the monitoring of pH from real samples including biological fluids.

Place, publisher, year, edition, pages
Elsevier, 2014
Keyword
Anion effect; Cobalt oxide nanostructures; Morphology; pH sensor; Potentiometric response
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-106984 (URN)10.1016/j.jelechem.2014.01.011 (DOI)000335112200011 ()
Available from: 2014-06-04 Created: 2014-06-02 Last updated: 2014-10-27Bibliographically approved
6. Synthesis of Three Dimensional Nickel Cobalt Oxide Nanoneedles on Nickel Foam, Their Characterization and Glucose Sensing Application
Open this publication in new window or tab >>Synthesis of Three Dimensional Nickel Cobalt Oxide Nanoneedles on Nickel Foam, Their Characterization and Glucose Sensing Application
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2014 (English)In: Sensors, ISSN 1424-8220, E-ISSN 1424-8220, Vol. 14, no 3, 5415-5425 p.Article in journal (Refereed) Published
Abstract [en]

In the present work, NiCo2O4 nanostructures are fabricated in three dimensions (3D) on nickel foam by the hydrothermal method. The nanomaterial was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The nanostructures exhibit nanoneedle-like morphology grown in 3D with good crystalline quality. The nanomaterial is composed of nickel, cobalt and oxygen atoms. By using the favorable porosity of the nanomaterial and the substrate itself, a sensitive glucose sensor is proposed by immobilizing glucose oxidase. The presented glucose sensor has shown linear response over a wide range of glucose concentrations from 0.005 mM to 15 mM with a sensitivity of 91.34 mV/decade and a fast response time of less than 10 s. The NiCo2O4 nanostructures-based glucose sensor has shown excellent reproducibility, repeatability and stability. The sensor showed negligible response to the normal concentrations of common interferents with glucose sensing, including uric acid, dopamine and ascorbic acid. All these favorable advantages of the fabricated glucose sensor suggest that it may have high potential for the determination of glucose in biological samples, food and other related areas.

Place, publisher, year, edition, pages
Basel, Switzerland: MDPI, 2014
Keyword
nickel cobalt oxide nanostructures; nickel foam; glucose sensor; potentiometric method
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-108230 (URN)10.3390/s140305415 (DOI)000336783300082 ()
Available from: 2014-06-26 Created: 2014-06-26 Last updated: 2017-12-05Bibliographically approved

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