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Synthesising Metal Oxide Materials and Their Composite Nanostructures for Sensing and Optoelectronic Device Applications
Linköping University, Department of Science and Technology, Physics and Electronics. Linköping University, The Institute of Technology.
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Research on nanomaterials has been revolutionized in the last few years because of the attractive properties they have in comparison to the bulk phase of similar materials. These properties are physical, chemical, catalytic and optical. Among these nanomaterials, the metal oxide nanostructures have become of particular interest to scientists for the development of different optical, biochemical and biomedical nanodevices. In the present research work using the advantageous features of nanotechnology, high performance nanodevices for optoelectronics with a wide band gap compound nanostructure and highly sensitive sensor devices have been demonstrated. The nanotechnology is used to fabricate sensitive and precise nanodevices based on nanomaterials for the application of sensing.

Among metal oxide nanostructures, ZnO, CuO and NiO are attractive materials because of their unique properties; their high surface area to volume ratio, their energy band gap of 3.37 eV, 1.2 eV and 3.7 eV, respectively, biocompatibility, high electron mobility, fast electron transfer rate and they are environmental-friendly in many applications. When used in sensor devices, nanomaterials have indicated high selectivity for possible use to detect the various analytes even in small volumes. Metal oxide nanostructures have shown to be good for optoelectronic nanodevices because of their electrical characteristics, high optical absorption and low-processing temperature.

In this thesis, the synthesis of different morphologies of metal oxide semiconductor nanostructures and their composite using the hydrothermal method are demonstrated for various applications. This thesis is divided into three parts:

In the first part of this research work, the fabrication of well-aligned ZnO nanorods using different concentrations of composite seed layer of inorganic and organic materials when using the hydrothermal growth method is presented. The effect of the composite seed layer on the alignment, density and optical properties of the grown ZnO nanorods is investigated (paper I). Utilizing the advantage of ZnO nanostructure, a comparative study of ZnO nanorods and thin films for chemical and biosensing application was carried out. The ZnO nanorods and thin films were functionalized with strontium ionophore membrane, immobilized the galactose oxidase and lactate oxidase for determining the strontium ions, D-galactose and L-lactic acid, respectively (paper II).

In the second part, the effects of different urea concentrations on the morphology of CuO nanostructures is studied as described in paper III. Moreover, CuO nanoflowers were functionalized with cadmium ion ionophore for the detection of Cd ions, while CuO nanosheets were grown by the low temperature growth method and were used for the development of a nonenzymatic glucose sensor, respectively (Paper IV).

In the last part of this thesis, composite nanostructures of CuO/ZnO and NiO/ZnO were applied to develop dopamine sensor and fast sensitive UV photodetector, respectively. A nanohybrid of CuO/ZnO nanostructure was used as a non-enzymatic electrode to detect dopamine by cyclic voltammetry (CV) and amperometric techniques (Paper V). In paper VI, we have demonstrated a strong UV absorption from ZnO nano-sheets achieved by the supramoleculesassisted growth solution using the hydrothermal method. The synthesized nanomaterial was used in the fabrication of UV photodetector based on p-NiO/ n-ZnO heterostructures.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2014. , 56 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1628
Keyword [en]
Hydrothermal method; metal oxide nanostructure; composite seed solution; wellaligned ZnO nanorods; composite structures; glucose and dopamine non-enzymatic sensors; heavy metals; supramolecular; UV photodetector sensor
National Category
Physical Sciences Electrical Engineering, Electronic Engineering, Information Engineering
Identifiers
URN: urn:nbn:se:liu:diva-112865DOI: 10.3384/diss.diva-112865ISBN: 978-91-7519-207-9 (print)OAI: oai:DiVA.org:liu-112865DiVA: diva2:773124
Public defence
2015-01-19, K3, Kåkenhus, Campus Norrköping, Linköpings universitet, Norrköping, 10:15 (English)
Opponent
Supervisors
Available from: 2014-12-18 Created: 2014-12-18 Last updated: 2015-01-14Bibliographically approved
List of papers
1. Fabrication of Well-Aligned ZnO Nanorods Using a Composite Seed Layer of ZnO Nanoparticles and Chitosan Polymer
Open this publication in new window or tab >>Fabrication of Well-Aligned ZnO Nanorods Using a Composite Seed Layer of ZnO Nanoparticles and Chitosan Polymer
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2013 (English)In: Materials, ISSN 1996-1944, E-ISSN 1996-1944, Vol. 6, no 10, 4361-4374 p.Article in journal (Refereed) Published
Abstract [en]

In this study, by taking the advantage of both inorganic ZnO nanoparticles and the organic material chitosan as a composite seed layer, we have fabricated well-aligned ZnO nanorods on a gold-coated glass substrate using the hydrothermal growth method. The ZnO nanoparticles were characterized by the Raman spectroscopic techniques, which showed the nanocrystalline phase of the ZnO nanoparticles. Different composites of ZnO nanoparticles and chitosan were prepared and used as a seed layer for the fabrication of well-aligned ZnO nanorods. Field emission scanning electron microscopy, energy dispersive X-ray, high-resolution transmission electron microscopy, X-ray diffraction, and infrared reflection absorption spectroscopic techniques were utilized for the structural characterization of the ZnO nanoparticles/chitosan seed layer-coated ZnO nanorods on a gold-coated glass substrate. This study has shown that the ZnO nanorods are well-aligned, uniform, and dense, exhibit the wurtzite hexagonal structure, and are perpendicularly oriented to the substrate. Moreover, the ZnO nanorods are only composed of Zn and O atoms. An optical study was also carried out for the ZnO nanoparticles/chitosan seed layer-coated ZnO nanorods, and the obtained results have shown that the fabricated ZnO nanorods exhibit good crystal quality. This study has provided a cheap fabrication method for the controlled morphology and good alignment of ZnO nanorods, which is of high demand for enhancing the working performance of optoelectronic devices.

Place, publisher, year, edition, pages
MDPI, 2013
Keyword
ZnO nanoparticles; chitosan; ZnO nanorods; well-aligned; low-temperature growth
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-104420 (URN)10.3390/ma6104361 (DOI)000330295600005 ()
Available from: 2014-02-17 Created: 2014-02-17 Last updated: 2017-12-06Bibliographically approved
2. Comparative study of ZnO nanorods and thin films for chemical and biosensing applications and the development of ZnO nanorods based potentiometric strontium ion sensor
Open this publication in new window or tab >>Comparative study of ZnO nanorods and thin films for chemical and biosensing applications and the development of ZnO nanorods based potentiometric strontium ion sensor
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2013 (English)In: Applied Surface Science, ISSN 0169-4332, E-ISSN 1873-5584, Vol. 268, 37-43 p.Article in journal (Refereed) Published
Abstract [en]

In this study, the comparative study of ZnO nanorods and ZnO thin films were performed regarding the chemical and biosensing properties and also ZnO nanorods based strontium ion sensor is proposed. ZnO nanorods were grown on gold coated glass substrates by the hydrothermal growth method and the ZnO thin films were deposited by electro deposition technique. ZnO nanorods and thin films were characterised by field emission electron microscopy [FESEM] and X-ray diffraction [XRD] techniques and this study has shown that the grown nanostructures are highly dense, uniform and exhibited good crystal quality. Moreover, transmission electron microscopy [TEM] was used to investigate the quality of ZnO thin film and we observed that ZnO thin film was comprised of nano clusters. ZnO nanorods and thin films were functionalised with selective strontium ionophore salicylaldehyde thiosemicarbazone [ST] membrane, galactose oxidase, and lactate oxidase for the detection of strontium ion, galactose and l-lactic acid, respectively. The electrochemical response of both ZnO nanorods and thin films sensor devices was measured by using the potentiometric method. The strontium ion sensor has exhibited good characteristics with a sensitivity of 28.65 +/- 0.52 mV/decade, for a wide range of concentrations from 1.00 x 10(-6) to 5.00 x 10(-2) M, selectivity, reproducibility, stability and fast response time of 10.00 s. The proposed strontium ion sensor was used as indicator electrode in the potentiometric titration of strontium ion versus ethylenediamine tetra acetic acid [EDTA]. This comparative study has shown that ZnO nanorods possessed better performance with high sensitivity and low limit of detection due to high surface area to volume ratio as compared to the flat surface of ZnO thin films.

Place, publisher, year, edition, pages
Elsevier, 2013
Keyword
ZnO nanorods, ZnO thin film, Immobilisation, Galactose oxidase, Lactate oxidase, Strontium ionophore, Potentiometric technique
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-90674 (URN)10.1016/j.apsusc.2012.11.141 (DOI)000315330300007 ()
Available from: 2013-04-03 Created: 2013-04-03 Last updated: 2017-12-06
3. Urea Assisted Synthesis of Flower Like CuO Nanostructures and Their Chemical Sensing Application for the Determination of Cadmium Ions
Open this publication in new window or tab >>Urea Assisted Synthesis of Flower Like CuO Nanostructures and Their Chemical Sensing Application for the Determination of Cadmium Ions
2013 (English)In: Electroanalysis, ISSN 1040-0397, E-ISSN 1521-4109, Vol. 25, no 6, 1425-1432 p.Article in journal (Refereed) Published
Abstract [en]

The novel nanostructures of CuO with improved morphology are strongly required for the development of devices with enhanced performance. In this study flower like nanostructures of CuO are synthesized by hydrothermal method using urea as tuning material for the morphology of CuO during the growth process. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques were used for the characterization of these nanostructures. The nanostructures are highly dense, uniform and well aligned on the gold coated glass substrate. Moreover, CuO nanostructures exhibited pure phase of CuO. These novel CuO nanostructures were potentially used for the construction of cadmium ion sensor by functionalizing with tetrathia-12-crown-4 a selective cadmium ion ionophore. The proposed cadmium ion sensor has detected the wide range of cadmium ion concentrations from 1.0x10-9-1.0x10-1M with a sensitivity of 29.3 +/- 0.3mV/decade and also a fast response time of less than 10.0s is demonstrated. CuO nanostructures based cadmium ion selective electrode has also shown excellent reproducibility, repeatability, selectivity, and stability. The sensor electrode was also used as indicator electrode for the confirmation of practical utility and the obtained result describes the good behavior of the sensor in the potentiometric titration for the determination of cadmium ions.

Place, publisher, year, edition, pages
Wiley-VCH Verlag, 2013
Keyword
Urea; Flower like morphology of CuO; Potentiometric response; Cadmium ions; Output response; Nanostructures
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-96119 (URN)10.1002/elan.201200660 (DOI)000320193100013 ()
Available from: 2013-08-14 Created: 2013-08-14 Last updated: 2017-12-06
4. Synthesis of Novel CuO Nanosheets and Their Non-Enzymatic Glucose Sensing Applications
Open this publication in new window or tab >>Synthesis of Novel CuO Nanosheets and Their Non-Enzymatic Glucose Sensing Applications
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2013 (English)In: Sensors, ISSN 1424-8220, E-ISSN 1424-8220, Vol. 13, no 6, 7926-7938 p.Article in journal (Refereed) Published
Abstract [en]

Abstract: In this study, we have developed a sensitive and selective glucose sensor using novel CuO nanosheets which were grown on a gold coated glass substrate by a low temperature growth method. X-ray differaction (XRD) and scanning electron microscopy (SEM) techniques were used for the structural characterization of CuO nanostructures. CuO nanosheets are highly dense, uniform, and exhibited good crystalline array structure. X-ray photoelectron spectroscopy (XPS) technique was applied for the study of chemical composition of CuO nanosheets and the obtained information demonstrated pure phase CuO nanosheets. The novel CuO nanosheets were employed for the development of a sensitive and selective non-enzymatic glucose sensor. The measured sensitivity and a correlation coefficient are in order 5.20 × 102 µA/mMcm2 and 0.998, respectively. The proposed sensor is associated with several advantages such as low cost, simplicity, high stability, reproducibility and selectivity for the quick detection of glucose.

Place, publisher, year, edition, pages
Basel, Switzerland: MDPI, 2013
Keyword
CuO nanosheets; hydrothermal growth method; non-enzymatic glucose sensor; selectivity; reproducibility
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-96478 (URN)10.3390/s130607926 (DOI)000320767600059 ()
Available from: 2013-08-23 Created: 2013-08-20 Last updated: 2017-12-06Bibliographically approved
5. An Electrochemical Dopamine Sensor Based on the ZnO/CuO Nanohybrid Structures
Open this publication in new window or tab >>An Electrochemical Dopamine Sensor Based on the ZnO/CuO Nanohybrid Structures
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2014 (English)In: Journal of Nanoscience and Nanotechnology, ISSN 1533-4880, E-ISSN 1533-4899, Vol. 14, no 9, 6646-6652 p.Article in journal (Refereed) Published
Abstract [en]

The selective detection of dopamine (DA) is of great importance in the modern medicine because dopamine is one of the main regulators in human behaviour. In this study, ZnO/CuO nanohybrid structures, grown on the gold coated glass substrate, have been investigated as a novel electrode material for the electrochemical detection of dopamine. Scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques were used for the material characterization and the obtained results are in good agreement. The selective determination of dopamine was demonstrated by cyclic voltammetry (CV) and amperometric experiments. The amperometric response was linear for dopamine concentrations between 1.0 x 10(-3) and 8.0 mM with a sensitivity of 90.9 mu A mM(-1) cm(-2). The proposed dopamine biosensor is very stable, selective over common interferents as glucose, uric acid and ascorbic acid, and also good reproducibility was observed for seven electrodes. Moreover, the dopamine sensor exhibited a fast response time of less than 10 s. The wide range and acceptable sensitivity of the presented dopamine sensor provide the possible application in analysing the dopamine from the real samples.

Place, publisher, year, edition, pages
American Scientific Publishers, 2014
Keyword
Dopamine; ZnO/CuO Nanohybrid Structures; Cyclic Voltammetry; Amperometry
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-107432 (URN)10.1166/jnn.2014.9367 (DOI)000335873900020 ()
Available from: 2014-06-12 Created: 2014-06-12 Last updated: 2017-12-05Bibliographically approved
6. Supramolecules-assisted ZnO nanostructures growth and their UV photodetector application
Open this publication in new window or tab >>Supramolecules-assisted ZnO nanostructures growth and their UV photodetector application
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2015 (English)In: Solid State Sciences, ISSN 1293-2558, E-ISSN 1873-3085, Vol. 41, 14-18 p.Article in journal (Refereed) Published
Abstract [en]

Zinc oxide (ZnO) nanosheets, nickel oxide (NiO) nanoflowers and their nanocomposite were grown on the fluorine doped tin oxide (FTO) substrate. The supramolecules-assisted ZnO growth by a hydrothermal method used to tune the morphology of the grown ZnO nanostructures to nanosheets morphology. The synthesis, purity and the optical properties of the grown material were characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), UV-visible spectrometry and photoluminescence (PL) analysis. The current-voltage (I-V) characterization of the ZnO/NiO heterojunction was performed at room temperature and showed an obvious nonlinear and rectifying response. A strong UV absorption with fast switching was observed from the ZnO/NiO composite heterojunction. The proposed UV photodetector based on this nano-composite is more stable, possesses fast rising and decaying time response approximately 100 ms and low leakage current was investigated. The findings indicate that the importance of the use of controlled nanostructures morphology for developing efficient nanodevices for various applications

Place, publisher, year, edition, pages
Elsevier, 2015
Keyword
ZnO/NiO nano-composite; UV absorption ZnO; nano-heterojunction; UV photodetector
National Category
Physical Sciences Electrical Engineering, Electronic Engineering, Information Engineering
Identifiers
urn:nbn:se:liu:diva-112863 (URN)10.1016/j.solidstatesciences.2015.01.011 (DOI)000350888800003 ()
Note

On the day of the defence date the status of this article was Manuscript.

Available from: 2014-12-18 Created: 2014-12-18 Last updated: 2017-12-05Bibliographically approved

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