Synthesis and evaluation of pyrene grafted onto zinc oxide nanoparticles for the removal of organic contaminants from wastewater
- Authors: Samuel, Zipho
- Date: 2022-03
- Subjects: Land treatment of wastewater , Zinc oxide , Water pollution control industry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10353/27754 , vital:69407
- Description: Drinking water scarcity is a global crisis even though water covers about three quarters of the earth. One of the major causes of this scarcity is water pollution, which is a result of human activities. This has been noticed and reported for a number of years but is still unsolved and intensifying. Hence, scientists are busy trying to find solutions to this global menace. In this study, zinc oxide nanoparticles were synthesised via co-precipitation, a cost reasonable method and functionalized by grafting a pyrene ligand on its surface in order to provide a scaffold to which many other functionalities can be adsorbed. By so doing, the efficiency and capacity of bare nanoparticles is improved. The synthesised pyrene ligand was successfully characterised with nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscope (FTIR). The adsorbent was characterized using X-ray diffractometer (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), FTIR, energy dispersive x-ray (EDX) and thermogravimetric analyzer (TGA). The choice of zinc oxide nanoparticles as preferred adsorbent was due to their exceptional properties including large surface area, thermal and chemical stabilities. These properties are the reason zinc oxide nanoparticles possess high adsorption efficiency and capacity. The results of characterization indicated a decreased particle size and improved thermal stabilities of the pyrene grafted zinc oxide nanoparticles compared to the zinc oxide nanoparticles, showing that this material can be employed even at higher temperatures. The average particle size of the bare nanoparticles decreased from 290 to 181 nm after functionalization. Thermal stability increased from 550oC in the bare nanoparticles to 650oC in the functionalized nanoparticles. Characteristic reflections of zinc oxide nanoparticles in the XRD analysis were maintained even after functionalization However, diffractogram roughness was noticed for the functionalized nanoparticles due to the introduction of the amorphous layer from the ligand. This novel material was employed for the removal of an herbicide, simazine as well as two dyes, methyl violet and brilliant green from aqueous solutions by batch adsorption experiments. The kinetics and isotherm studies of the different adsorption processes were carried out by using three of the commonly used kinetic and isotherm models (pseudo-first order, intraparticle diffusion and pseudo-second order) and (Langmuir, Temkin isotherms and Freundlich) respectively. From all batch adsorption experiments conducted for simazine removal, the adsorbent showed effectiveness and high adsorption capacity for the removal of simazine. The highest observed efficiency and capacity were 71.3 percent and 137 mg/g respectively at pH equals 2, time equals 60 minutes, adsorbent dose equals 20 mg and adsorbate conc equals 0. 281 mg/L. Kinetics study for the adsorption of simazine favoured pseudo-first order. However, Langmuir isotherm could also be applicable to understand the adsorption process. The material also showed reusability potential of up to three cycles for this contaminant indicating that this material can be re-used. In the case of the removal of methyl violet from aqueous solution, the adsorbent showed a reasonable adsorption maximum capacity (qmax) (31.5 mg/g) at contact time equals 360 min, adsorbent dose approximately equals 40 mg, temperature equals 20 plus 2oC and pH equals 6.5, when compared to other adsorbents previously reported for the removal of methyl violet (MV) in literature. Kinetics and isotherm studies indicated that the process for the removal of this pollutant with this pyrene grafted onto zinc oxide nanoparticles proceeded via pseudo-first order (R2 equals 0.931) and Langmuir isotherm models (R2 equals 0.980) respectively. These results indicated that this material could serve as alternate material to already established materials for the removal of recalcitrant organic pollutants from aqueous solutions. Moreover, the adsorbent also showed reusability potential for this contaminant. Similarly, the adsorbent showed high removal efficiency and capacity in all batch adsorption experiments for brilliant green (BG) adsorption. The highest adsorption efficiency of 88.8 percent was accomplished with 79.8 mg at pH 6.50 and temperature of 20 equals 2oC within 360 minutes. BG adsorption rate mechanism was best explained by the pseudo-first order kinetic model (R2 equals 0.903). Dye adsorption behaviour was best explained using Langmuir isotherm (R2 equals 0.980). Reusability of the adsorbent showed that the adsorbent is efficient after three runs. The overall results of adsorption by a way of comparison of the adsorption capacity of this novel material with respect to the contaminants is in this trend: brilliant green greater methyl violet greater simazine. This study indicates that this novel material can serve as new material for the removal of herbicides and dyes as well as vast variety of pollutants from wastewater considering its high adsorption efficiency and its recyclability. Thus, industries can explore the use of this material for the removal of varying pollutants from wastewater. , Thesis (MSc) -- Faculty of Science and Agriculture, 2022
- Full Text:
- Date Issued: 2022-03
- Authors: Samuel, Zipho
- Date: 2022-03
- Subjects: Land treatment of wastewater , Zinc oxide , Water pollution control industry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10353/27754 , vital:69407
- Description: Drinking water scarcity is a global crisis even though water covers about three quarters of the earth. One of the major causes of this scarcity is water pollution, which is a result of human activities. This has been noticed and reported for a number of years but is still unsolved and intensifying. Hence, scientists are busy trying to find solutions to this global menace. In this study, zinc oxide nanoparticles were synthesised via co-precipitation, a cost reasonable method and functionalized by grafting a pyrene ligand on its surface in order to provide a scaffold to which many other functionalities can be adsorbed. By so doing, the efficiency and capacity of bare nanoparticles is improved. The synthesised pyrene ligand was successfully characterised with nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscope (FTIR). The adsorbent was characterized using X-ray diffractometer (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), FTIR, energy dispersive x-ray (EDX) and thermogravimetric analyzer (TGA). The choice of zinc oxide nanoparticles as preferred adsorbent was due to their exceptional properties including large surface area, thermal and chemical stabilities. These properties are the reason zinc oxide nanoparticles possess high adsorption efficiency and capacity. The results of characterization indicated a decreased particle size and improved thermal stabilities of the pyrene grafted zinc oxide nanoparticles compared to the zinc oxide nanoparticles, showing that this material can be employed even at higher temperatures. The average particle size of the bare nanoparticles decreased from 290 to 181 nm after functionalization. Thermal stability increased from 550oC in the bare nanoparticles to 650oC in the functionalized nanoparticles. Characteristic reflections of zinc oxide nanoparticles in the XRD analysis were maintained even after functionalization However, diffractogram roughness was noticed for the functionalized nanoparticles due to the introduction of the amorphous layer from the ligand. This novel material was employed for the removal of an herbicide, simazine as well as two dyes, methyl violet and brilliant green from aqueous solutions by batch adsorption experiments. The kinetics and isotherm studies of the different adsorption processes were carried out by using three of the commonly used kinetic and isotherm models (pseudo-first order, intraparticle diffusion and pseudo-second order) and (Langmuir, Temkin isotherms and Freundlich) respectively. From all batch adsorption experiments conducted for simazine removal, the adsorbent showed effectiveness and high adsorption capacity for the removal of simazine. The highest observed efficiency and capacity were 71.3 percent and 137 mg/g respectively at pH equals 2, time equals 60 minutes, adsorbent dose equals 20 mg and adsorbate conc equals 0. 281 mg/L. Kinetics study for the adsorption of simazine favoured pseudo-first order. However, Langmuir isotherm could also be applicable to understand the adsorption process. The material also showed reusability potential of up to three cycles for this contaminant indicating that this material can be re-used. In the case of the removal of methyl violet from aqueous solution, the adsorbent showed a reasonable adsorption maximum capacity (qmax) (31.5 mg/g) at contact time equals 360 min, adsorbent dose approximately equals 40 mg, temperature equals 20 plus 2oC and pH equals 6.5, when compared to other adsorbents previously reported for the removal of methyl violet (MV) in literature. Kinetics and isotherm studies indicated that the process for the removal of this pollutant with this pyrene grafted onto zinc oxide nanoparticles proceeded via pseudo-first order (R2 equals 0.931) and Langmuir isotherm models (R2 equals 0.980) respectively. These results indicated that this material could serve as alternate material to already established materials for the removal of recalcitrant organic pollutants from aqueous solutions. Moreover, the adsorbent also showed reusability potential for this contaminant. Similarly, the adsorbent showed high removal efficiency and capacity in all batch adsorption experiments for brilliant green (BG) adsorption. The highest adsorption efficiency of 88.8 percent was accomplished with 79.8 mg at pH 6.50 and temperature of 20 equals 2oC within 360 minutes. BG adsorption rate mechanism was best explained by the pseudo-first order kinetic model (R2 equals 0.903). Dye adsorption behaviour was best explained using Langmuir isotherm (R2 equals 0.980). Reusability of the adsorbent showed that the adsorbent is efficient after three runs. The overall results of adsorption by a way of comparison of the adsorption capacity of this novel material with respect to the contaminants is in this trend: brilliant green greater methyl violet greater simazine. This study indicates that this novel material can serve as new material for the removal of herbicides and dyes as well as vast variety of pollutants from wastewater considering its high adsorption efficiency and its recyclability. Thus, industries can explore the use of this material for the removal of varying pollutants from wastewater. , Thesis (MSc) -- Faculty of Science and Agriculture, 2022
- Full Text:
- Date Issued: 2022-03
On the development of ZnO nanorods on silicon substrate for light-emitting diode applications
- Djiokap, Stive Roussel Tankio
- Authors: Djiokap, Stive Roussel Tankio
- Date: 2018
- Subjects: Zinc oxide , Chemical reactions , Compound semiconductors
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/29973 , vital:30802
- Description: The interest in zinc oxide (ZnO), a promising material for blue/ultraviolet light emitting devices, arises from its large exciton binding energy (60 meV). The main challenge associated with this promising compound semiconductor, however, arises from the difficulty to achieve stable and/or reproducible p-type doping. Since silicon (Si) technology still dominates the semiconductor industry, the objective of this thesis is to probe into the possibility of using ZnO nanorods (NRs) on p-type silicon for opto-electronic devices. ZnO NRs have been grown on seeded Si, as well as on nickel oxide (NiO) and aluminum nitride (AlN) coated Si, using a two-step chemical bath deposition (CBD) process. Various techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and transmission electron microscopy (TEM), have been used to characterize the samples. The electrical characteristics of the heterojunction between the substrate and the ZnO nanostructures were evaluated by current-voltage (I-V) and capacitance-voltage (C-V) measurements. SEM and XRD studies have confirmed that, irrespective of the orientation of the Si substrate (Si (100) and Si (111)), the two-step CBD process yielded NRs that crystallised in the wurtzite structure and exhibited a hexagonal shape. Most of the rods developed perpendicularly to the surface of the substrate, with the orientation and distribution of the rods dictated by the seed layer density. Similarly, irrespective of the substrate, the luminescence of the ZnO nanostructures is dominated by near band edge (NBE) emission in the UV region (~ 3.29 eV) and deep level emission (DLE) in the visible region (2 eV to 2.6 eV). Annealing at moderate temperatures (~ 300 °C) increased the NBE emission and decreased the DLE. The removal of surface adsorbed impurities and enhanced defect passivation by hydrogen are responsible for these changes. The diode characteristics of the ZnO/Si heterojunction was studied by I-V and C-V measurements. Rectification was observed when the Si substrate had a relatively low acceptor density of ~1016 cm-3, while diodes produced on substrate with p ~1018 cm-3 were ohmic. From the C-V analysis the donor density in the ZnO was deduced to be ~1018 cm-3. In the case of rectifying junctions, thermionic emission did not dominate the charge transport. The carrier transport mechanism was therefore probed by the temperature dependent I-V xiii measurements (100 K to 295 K). Defect-assisted multistep tunneling was deduced to dominate in the n-ZnO/p-Si diodes at low forward bias. The band alignment between n-ZnO and p-Si predicts a much smaller barrier for electrons than for holes at the interface, which results in recombination on the Si side of the junction for a forward-biased diode. NiO intermediate layers (formed on Si by the thermal oxidation of Ni) were used to reduce electron injection from ZnO into Si. Scanning probe microscopy (SPM) and XRD analysis showed that while the grain size of the poly-crystalline NiO increased with NiO film thickness, the orientation and distribution of the subsequently grown ZnO nanorods were unaffected by the underlying NiO layer. Also, the photoluminescence response of the ZnO rods remained unchanged. I-V measurements did illustrate rectifying behaviour, with both the forward and reverse currents strongly decreased due to the resistive nature of the NiO. In another attempt at confining electrons to the ZnO side of the junction, AlN-coated Si (111) was used as a substrate for ZnO nanorods. CBD parameters that normally yield nanorods resulted in a plate-like architecture of the ZnO. By modifying the ZnO seed density on the AlN/Si substrate, the rod-like morphology could be recovered. Both the forward and reverse current decreased in these diodes. From studies aimed at identifying the transport mechanism it was concluded that trap-assisted tunnelling, resulting from a high density of defects in the seed layer, dominates in these devices. In conclusion, while no ZnO electroluminescence could be achieved from any of the devices, this study provides insight into the transport mechanisms in n-ZnO/barrier/p-Si heterostructures and highlights the importance of the heterointerface quality for light emitting devices.
- Full Text:
- Date Issued: 2018
- Authors: Djiokap, Stive Roussel Tankio
- Date: 2018
- Subjects: Zinc oxide , Chemical reactions , Compound semiconductors
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/29973 , vital:30802
- Description: The interest in zinc oxide (ZnO), a promising material for blue/ultraviolet light emitting devices, arises from its large exciton binding energy (60 meV). The main challenge associated with this promising compound semiconductor, however, arises from the difficulty to achieve stable and/or reproducible p-type doping. Since silicon (Si) technology still dominates the semiconductor industry, the objective of this thesis is to probe into the possibility of using ZnO nanorods (NRs) on p-type silicon for opto-electronic devices. ZnO NRs have been grown on seeded Si, as well as on nickel oxide (NiO) and aluminum nitride (AlN) coated Si, using a two-step chemical bath deposition (CBD) process. Various techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and transmission electron microscopy (TEM), have been used to characterize the samples. The electrical characteristics of the heterojunction between the substrate and the ZnO nanostructures were evaluated by current-voltage (I-V) and capacitance-voltage (C-V) measurements. SEM and XRD studies have confirmed that, irrespective of the orientation of the Si substrate (Si (100) and Si (111)), the two-step CBD process yielded NRs that crystallised in the wurtzite structure and exhibited a hexagonal shape. Most of the rods developed perpendicularly to the surface of the substrate, with the orientation and distribution of the rods dictated by the seed layer density. Similarly, irrespective of the substrate, the luminescence of the ZnO nanostructures is dominated by near band edge (NBE) emission in the UV region (~ 3.29 eV) and deep level emission (DLE) in the visible region (2 eV to 2.6 eV). Annealing at moderate temperatures (~ 300 °C) increased the NBE emission and decreased the DLE. The removal of surface adsorbed impurities and enhanced defect passivation by hydrogen are responsible for these changes. The diode characteristics of the ZnO/Si heterojunction was studied by I-V and C-V measurements. Rectification was observed when the Si substrate had a relatively low acceptor density of ~1016 cm-3, while diodes produced on substrate with p ~1018 cm-3 were ohmic. From the C-V analysis the donor density in the ZnO was deduced to be ~1018 cm-3. In the case of rectifying junctions, thermionic emission did not dominate the charge transport. The carrier transport mechanism was therefore probed by the temperature dependent I-V xiii measurements (100 K to 295 K). Defect-assisted multistep tunneling was deduced to dominate in the n-ZnO/p-Si diodes at low forward bias. The band alignment between n-ZnO and p-Si predicts a much smaller barrier for electrons than for holes at the interface, which results in recombination on the Si side of the junction for a forward-biased diode. NiO intermediate layers (formed on Si by the thermal oxidation of Ni) were used to reduce electron injection from ZnO into Si. Scanning probe microscopy (SPM) and XRD analysis showed that while the grain size of the poly-crystalline NiO increased with NiO film thickness, the orientation and distribution of the subsequently grown ZnO nanorods were unaffected by the underlying NiO layer. Also, the photoluminescence response of the ZnO rods remained unchanged. I-V measurements did illustrate rectifying behaviour, with both the forward and reverse currents strongly decreased due to the resistive nature of the NiO. In another attempt at confining electrons to the ZnO side of the junction, AlN-coated Si (111) was used as a substrate for ZnO nanorods. CBD parameters that normally yield nanorods resulted in a plate-like architecture of the ZnO. By modifying the ZnO seed density on the AlN/Si substrate, the rod-like morphology could be recovered. Both the forward and reverse current decreased in these diodes. From studies aimed at identifying the transport mechanism it was concluded that trap-assisted tunnelling, resulting from a high density of defects in the seed layer, dominates in these devices. In conclusion, while no ZnO electroluminescence could be achieved from any of the devices, this study provides insight into the transport mechanisms in n-ZnO/barrier/p-Si heterostructures and highlights the importance of the heterointerface quality for light emitting devices.
- Full Text:
- Date Issued: 2018
Phthalocyanine-nanoparticle conjugates for photodynamic therapy of cancer and phototransformation of organic pollutants
- Authors: Khoza, Phindile Brenda
- Date: 2015
- Subjects: Phthalocyanines , Nanoparticles , Photochemotherapy , Cancer -- Chemotherapy , Zinc oxide , Photocatalysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4538 , http://hdl.handle.net/10962/d1017918
- Description: The synthesis and extensive spectroscopical characterization of novel phthalocyanines are reported. The new compounds were characterized by elemental analysis, FT-IR, ¹HNMR, mass spectrometry and UV–Vis spectroscopy. The new phthalocyanines showed remarkable photophysicochemical behaviour. The novel phthalocyanines were then conjugated to nanoparticles, silver and ZnO. The coupling of the novel Pcs to nanoparticles was through covalent bonding and ligand exchange. These conjugates were supported onto electrospun polystyrene fibers and chitosan microbeads for use as photocatalysts. The efficiency of the immobilized Pcs and Pc-nanoparticles was assessed by the phototrasfromation of organic pollutants, methyl orange and Rhodamine 6G as model dyes. Upon conjugating phthalocyanines to nanoparticles, there was a great increase in the rate of photodegradation of the model dyes. The photodynamic activity of the novel phthalocyanines upon conjugating to nanoparticles and selected targeting agents is also reported. The targeting agents employed in this study are folic acid and polylysine. Conjugating the phthalocyanines to folic acid or polylysine improved the solubility of the phthalocyanines in aqueous media. The potency of the conjugates was investigated on breast (MCF-7), prostate and melanoma cancer cell lines. The phthalocyanines showed no toxicity in the absence of light. However, upon illumination, a concentration dependent cellular decrease was observed.
- Full Text:
- Date Issued: 2015
- Authors: Khoza, Phindile Brenda
- Date: 2015
- Subjects: Phthalocyanines , Nanoparticles , Photochemotherapy , Cancer -- Chemotherapy , Zinc oxide , Photocatalysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4538 , http://hdl.handle.net/10962/d1017918
- Description: The synthesis and extensive spectroscopical characterization of novel phthalocyanines are reported. The new compounds were characterized by elemental analysis, FT-IR, ¹HNMR, mass spectrometry and UV–Vis spectroscopy. The new phthalocyanines showed remarkable photophysicochemical behaviour. The novel phthalocyanines were then conjugated to nanoparticles, silver and ZnO. The coupling of the novel Pcs to nanoparticles was through covalent bonding and ligand exchange. These conjugates were supported onto electrospun polystyrene fibers and chitosan microbeads for use as photocatalysts. The efficiency of the immobilized Pcs and Pc-nanoparticles was assessed by the phototrasfromation of organic pollutants, methyl orange and Rhodamine 6G as model dyes. Upon conjugating phthalocyanines to nanoparticles, there was a great increase in the rate of photodegradation of the model dyes. The photodynamic activity of the novel phthalocyanines upon conjugating to nanoparticles and selected targeting agents is also reported. The targeting agents employed in this study are folic acid and polylysine. Conjugating the phthalocyanines to folic acid or polylysine improved the solubility of the phthalocyanines in aqueous media. The potency of the conjugates was investigated on breast (MCF-7), prostate and melanoma cancer cell lines. The phthalocyanines showed no toxicity in the absence of light. However, upon illumination, a concentration dependent cellular decrease was observed.
- Full Text:
- Date Issued: 2015
Growth and characterization of ZnO nanorods using chemical bath deposition
- Authors: Urgessa, Zelalem Nigussa
- Date: 2012
- Subjects: Zinc oxide , Photoluminescence , Semiconductor nanocrystals , Semiconductors -- Materials , Chemical reactions
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10559 , http://hdl.handle.net/10948/d1021124 , http://hdl.handle.net/10948/d1021119
- Description: Semiconductor devices are commonplace in every household. One application of semiconductors in particular, namely solid state lighting technology, is destined for a bright future. To this end, ZnO nanostructures have gained substantial interest in the research community, in part because of its requisite large direct band gap. Furthermore, the stability of the exciton (binding energy 60 meV) in this material, can lead to lasing action based on exciton recombination and possibly exciton interaction, even above room temperature. Therefore, it is very important to realize controllable growth of ZnO nanostructures and investigate their properties. The main motivation for this thesis is not only to successfully realize the controllable growth of ZnO nanorods, but also to investigate the structure, optical and electrical properties in detail by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy (steady state and time resolved) and X-ray diffraction (XRD). Furthermore, strong rectification in the ZnO/p-Si heterojunction is demonstrated. Nanorods have been successfully synthesized on silicon by a two-step process, involving the pre-coating of the substrate by a seed layer, followed by the chemical bath deposition of the nanorods. ZnO seed layers with particle sizes of about 5 nm are achieved by the thermal decomposition of zinc acetate dihydrate dissolved in ethanol. The effects of the seed layer density on the distribution, alignment and uniformity of subsequently grown nanorods were studied. The aspect ratio, orientation and distribution of nanorods are shown to be well controlled through adjusting the density of the ZnO nanoparticles pre-coated onto the substrates. It is shown that the seed layer is a prerequisite for the growth of well aligned ZnO nanorods on lattice mismatched Si substrate. The influence of various nanorod growth parameters on the morphology, optical and electrical properties of the nanorods were also systematically studied. These include the oxygen to zinc molar ratio, the pH of the growth solution, the concentration of the reactants, the growth temperature and growth time, different hydroxide precursors and the addition of surface passivating agents to the growth solution. By controlling these xii parameters different architectures of nanostructures, like spherical particles, well aligned nanorods, nanoflowers and thin films of different thicknesses are demonstrated. A possible growth mechanism for ZnO nanostructures in solution is proposed. XRD indicated that all the as-grown nanostructures produced above 45 C crystallize in the wurtzite structure and post growth annealing does not significantly enhance the crystalline quality of the material. In material grown at lower temperature, traces of zinc hydroxide were observed. The optical quality of the nanostructures was investigated using both steady-state PL and time-resolved (TR) PL from 4 K to room temperature. In the case of as-grown samples, both UV and defect related emissions have been observed for all nanostructures. The effect of post-growth annealing on the optical quality of the nanostructures was carefully examined. The effect of annealing in different atmospheres was also investigated. Regardless of the annealing environment annealing at a temperature as low as 300 C enhances the UV emission and suppresses defect related deep level emission. However, annealing above 500 C is required to out-diffuse hydrogen, the presence of which is deduced from the I4 line in the low temperature PL spectra of ZnO. TRPL was utilized to investigate lifetime decay profiles of nanorods upon different post growth treatments. The bound exciton lifetime strongly depends on the post-growth annealing temperature: the PL decay time is much faster for as grown rods, confirming the domination of surface assisted recombination. In general, the PL analysis showed that the PL of nanorods have the same characteristics as that of bulk ZnO, except for the stronger contribution from surface related bound excitons in the former case. Surface adsorbed impurities causing depletion and band bending in the near surface region is implied from both time resolved and steady state PL. Finally, although strong rectification in the ZnO/p-Si heterojunction is illustrated, no electroluminescence has been achieved. This is explained in terms of the band offset between ZnO and Si and interfacial states. Different schemes are proposed to improve the performance of ZnO/Si heterojunction light emitting devices.
- Full Text:
- Date Issued: 2012
- Authors: Urgessa, Zelalem Nigussa
- Date: 2012
- Subjects: Zinc oxide , Photoluminescence , Semiconductor nanocrystals , Semiconductors -- Materials , Chemical reactions
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10559 , http://hdl.handle.net/10948/d1021124 , http://hdl.handle.net/10948/d1021119
- Description: Semiconductor devices are commonplace in every household. One application of semiconductors in particular, namely solid state lighting technology, is destined for a bright future. To this end, ZnO nanostructures have gained substantial interest in the research community, in part because of its requisite large direct band gap. Furthermore, the stability of the exciton (binding energy 60 meV) in this material, can lead to lasing action based on exciton recombination and possibly exciton interaction, even above room temperature. Therefore, it is very important to realize controllable growth of ZnO nanostructures and investigate their properties. The main motivation for this thesis is not only to successfully realize the controllable growth of ZnO nanorods, but also to investigate the structure, optical and electrical properties in detail by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy (steady state and time resolved) and X-ray diffraction (XRD). Furthermore, strong rectification in the ZnO/p-Si heterojunction is demonstrated. Nanorods have been successfully synthesized on silicon by a two-step process, involving the pre-coating of the substrate by a seed layer, followed by the chemical bath deposition of the nanorods. ZnO seed layers with particle sizes of about 5 nm are achieved by the thermal decomposition of zinc acetate dihydrate dissolved in ethanol. The effects of the seed layer density on the distribution, alignment and uniformity of subsequently grown nanorods were studied. The aspect ratio, orientation and distribution of nanorods are shown to be well controlled through adjusting the density of the ZnO nanoparticles pre-coated onto the substrates. It is shown that the seed layer is a prerequisite for the growth of well aligned ZnO nanorods on lattice mismatched Si substrate. The influence of various nanorod growth parameters on the morphology, optical and electrical properties of the nanorods were also systematically studied. These include the oxygen to zinc molar ratio, the pH of the growth solution, the concentration of the reactants, the growth temperature and growth time, different hydroxide precursors and the addition of surface passivating agents to the growth solution. By controlling these xii parameters different architectures of nanostructures, like spherical particles, well aligned nanorods, nanoflowers and thin films of different thicknesses are demonstrated. A possible growth mechanism for ZnO nanostructures in solution is proposed. XRD indicated that all the as-grown nanostructures produced above 45 C crystallize in the wurtzite structure and post growth annealing does not significantly enhance the crystalline quality of the material. In material grown at lower temperature, traces of zinc hydroxide were observed. The optical quality of the nanostructures was investigated using both steady-state PL and time-resolved (TR) PL from 4 K to room temperature. In the case of as-grown samples, both UV and defect related emissions have been observed for all nanostructures. The effect of post-growth annealing on the optical quality of the nanostructures was carefully examined. The effect of annealing in different atmospheres was also investigated. Regardless of the annealing environment annealing at a temperature as low as 300 C enhances the UV emission and suppresses defect related deep level emission. However, annealing above 500 C is required to out-diffuse hydrogen, the presence of which is deduced from the I4 line in the low temperature PL spectra of ZnO. TRPL was utilized to investigate lifetime decay profiles of nanorods upon different post growth treatments. The bound exciton lifetime strongly depends on the post-growth annealing temperature: the PL decay time is much faster for as grown rods, confirming the domination of surface assisted recombination. In general, the PL analysis showed that the PL of nanorods have the same characteristics as that of bulk ZnO, except for the stronger contribution from surface related bound excitons in the former case. Surface adsorbed impurities causing depletion and band bending in the near surface region is implied from both time resolved and steady state PL. Finally, although strong rectification in the ZnO/p-Si heterojunction is illustrated, no electroluminescence has been achieved. This is explained in terms of the band offset between ZnO and Si and interfacial states. Different schemes are proposed to improve the performance of ZnO/Si heterojunction light emitting devices.
- Full Text:
- Date Issued: 2012
Development of MgZnO-grown MOCVD for UV Photonic applications
- Authors: Talla, Kharouna
- Date: 2011
- Subjects: Photoluminescence , Photonics , Zinc oxide
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10537 , http://hdl.handle.net/10948/d1012585 , Photoluminescence , Photonics , Zinc oxide
- Description: MgxZn1-xO has emerged as a material of great technological importance. Having a direct energy band gap that is tunable throughout much of the ultraviolet (UV) region of the spectrum from the near-UV (~370 nm) to the deep-UV (~176 nm), this compound is of interest for a variety of optoelectronic devices operating in this part of the electromagnetic spectrum. MgxZn1-xO offers advantages over the more mature compound semiconductor AlGaN which stem mainly from the unusually high exciton binding energy (60 meV in ZnO). In this study the growth of ZnO and MgxZn1-xO thin films using metal organic chemical vapour deposition (MOCVD) is systematically investigated. The films are mainly grown on c-Al2O3 and Si (100) and characterized using various techniques, such as photoluminescence (PL), x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and auger electron spectroscopy (AES). The optical and the structural properties are essentially inspected in order to improve their quality. In this thesis the optimisation of ZnO grown using oxygen gas as a new oxidant in our reactor is investigated. The growth temperature and VI/II ratio are varied in order to find optimum parameters giving high quality layers. The effects of Si (100), Si (111), c- and r-sapphire, glass, GaAs and ZnO substrates on the optical, structural and morphological properties of ZnO thin films grown with tert-butanol (TBOH) is examined. Similar morphologies are observed for all substrates, with the films comprising hexagonal columns having cone shaped ends. The photoluminescence spectra are similar, but the various transitions have different relative intensities. It is clear that the different substrates influence neither the orientation of the films, nor the surface morphology, significantly. The photoluminescence hints at larger stacking fault densities in films grown on silicon and glass, however, as evidenced by stronger basal plane stacking fault-related luminescence at ~3.319 eV in the relevant low temperature photoluminescence spectra. The morphology changes with Mg incorporation, from hexagonal columnar structures to cubic faceted columns. From PL, the full with at half maximum is found to gradually increase with Mg content due to alloy broadening. The deep level emission (DLE) is observed to shift with Mg content. By changing the Mg content, the band gap of MgxZn1-xO film is tuned by ~450 meV, which provides an excellent opportunity for band gap engineering for optoelectronic applications. The c-lattice constant of ZnO (5.205 Å) decreases by only 0.6% when the Mg content reaches x=0.39. The introduction of Mg into ZnO is shown to increase the relative PL intensity of stacking fault-related transitions (at 3.314 eV for ZnO). This becomes the dominant near band edge emission. Using TEM a thin Mg rich layer is observed at the interface between the film and the Si or Al2O3. Temperature dependent PL measurements on layers with low Mg concentration (x=0.05 and 0.1) show that the main bound exciton peak exhibits an “s-shaped” temperature dependence, characteristic of localization in a disordered alloy. The origin of the PL line broadening of MgxZn1-xO (x≤0.04) is also analyzed with respect to alloy broadening, taking into account a random cation distribution and alloy clustering. The influence of various MOCVD growth parameters such as growth temperature and VI/II ratio is studied. Varying the temperature from 280 ˚C to 580 ˚C reveals strong morphological changes and optical degradation of the films. Low (<280 ˚C) and high (>580 ˚C) growth temperatures reduce the Mg incorporation. High VI/II ratios also decrease the Mg incorporation, as evidenced by the red-shift of the donor bound exciton (D°X) line. This is ascribed to a stronger premature reaction between (MeCp)2Mg and the oxidant or a preferential heterogeneous interaction between the Mg and oxygen species on the growth front. For both oxidizing agents (O2 and TBOH), the growth at 420 ˚C and a VI-II ratio of 60 on c-Al2O3 gave optimal quality layers in terms of their optical and structural quality. A comparison of films grown using TBOH and O2 gas as oxidizing agent shows no major difference in terms of Mg incorporation. The effect of annealing, the inclusion of a buffer layer and the influence of growth rate on the properties MgxZn1-xO thin films are also reported.
- Full Text:
- Date Issued: 2011
- Authors: Talla, Kharouna
- Date: 2011
- Subjects: Photoluminescence , Photonics , Zinc oxide
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10537 , http://hdl.handle.net/10948/d1012585 , Photoluminescence , Photonics , Zinc oxide
- Description: MgxZn1-xO has emerged as a material of great technological importance. Having a direct energy band gap that is tunable throughout much of the ultraviolet (UV) region of the spectrum from the near-UV (~370 nm) to the deep-UV (~176 nm), this compound is of interest for a variety of optoelectronic devices operating in this part of the electromagnetic spectrum. MgxZn1-xO offers advantages over the more mature compound semiconductor AlGaN which stem mainly from the unusually high exciton binding energy (60 meV in ZnO). In this study the growth of ZnO and MgxZn1-xO thin films using metal organic chemical vapour deposition (MOCVD) is systematically investigated. The films are mainly grown on c-Al2O3 and Si (100) and characterized using various techniques, such as photoluminescence (PL), x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and auger electron spectroscopy (AES). The optical and the structural properties are essentially inspected in order to improve their quality. In this thesis the optimisation of ZnO grown using oxygen gas as a new oxidant in our reactor is investigated. The growth temperature and VI/II ratio are varied in order to find optimum parameters giving high quality layers. The effects of Si (100), Si (111), c- and r-sapphire, glass, GaAs and ZnO substrates on the optical, structural and morphological properties of ZnO thin films grown with tert-butanol (TBOH) is examined. Similar morphologies are observed for all substrates, with the films comprising hexagonal columns having cone shaped ends. The photoluminescence spectra are similar, but the various transitions have different relative intensities. It is clear that the different substrates influence neither the orientation of the films, nor the surface morphology, significantly. The photoluminescence hints at larger stacking fault densities in films grown on silicon and glass, however, as evidenced by stronger basal plane stacking fault-related luminescence at ~3.319 eV in the relevant low temperature photoluminescence spectra. The morphology changes with Mg incorporation, from hexagonal columnar structures to cubic faceted columns. From PL, the full with at half maximum is found to gradually increase with Mg content due to alloy broadening. The deep level emission (DLE) is observed to shift with Mg content. By changing the Mg content, the band gap of MgxZn1-xO film is tuned by ~450 meV, which provides an excellent opportunity for band gap engineering for optoelectronic applications. The c-lattice constant of ZnO (5.205 Å) decreases by only 0.6% when the Mg content reaches x=0.39. The introduction of Mg into ZnO is shown to increase the relative PL intensity of stacking fault-related transitions (at 3.314 eV for ZnO). This becomes the dominant near band edge emission. Using TEM a thin Mg rich layer is observed at the interface between the film and the Si or Al2O3. Temperature dependent PL measurements on layers with low Mg concentration (x=0.05 and 0.1) show that the main bound exciton peak exhibits an “s-shaped” temperature dependence, characteristic of localization in a disordered alloy. The origin of the PL line broadening of MgxZn1-xO (x≤0.04) is also analyzed with respect to alloy broadening, taking into account a random cation distribution and alloy clustering. The influence of various MOCVD growth parameters such as growth temperature and VI/II ratio is studied. Varying the temperature from 280 ˚C to 580 ˚C reveals strong morphological changes and optical degradation of the films. Low (<280 ˚C) and high (>580 ˚C) growth temperatures reduce the Mg incorporation. High VI/II ratios also decrease the Mg incorporation, as evidenced by the red-shift of the donor bound exciton (D°X) line. This is ascribed to a stronger premature reaction between (MeCp)2Mg and the oxidant or a preferential heterogeneous interaction between the Mg and oxygen species on the growth front. For both oxidizing agents (O2 and TBOH), the growth at 420 ˚C and a VI-II ratio of 60 on c-Al2O3 gave optimal quality layers in terms of their optical and structural quality. A comparison of films grown using TBOH and O2 gas as oxidizing agent shows no major difference in terms of Mg incorporation. The effect of annealing, the inclusion of a buffer layer and the influence of growth rate on the properties MgxZn1-xO thin films are also reported.
- Full Text:
- Date Issued: 2011
Photoluminescence study of ZnO doped with nitrogen and arsenic
- Authors: Dangbegnon, Julien Kouadio
- Date: 2010
- Subjects: Photoluminescence , Zinc oxide , Nitrogen , Arsenic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10518 , http://hdl.handle.net/10948/1216 , Photoluminescence , Zinc oxide , Nitrogen , Arsenic
- Description: In this work, the optical properties of ZnO doped with arsenic and nitrogen were studied. The ZnO samples were grown by Metalorganic Chemical Vapor Deposition (MOCVD). The solubility of nitrogen in the ZnO films, as well as its activation upon annealing, was also investigated. Hydrogen is known as a major source for passivation of the acceptors in ZnO:N. Therefore, it is crucial to dissociate the complex(es) formed by nitrogen and hydrogen and diffuse out the hydrogen in order to prevent the reformation of such complexes. High temperatures (≥ 600 C) are required for these purposes. In order to effectively remove the hydrogen impurities from the sample, it is important to know the optical fingerprints of hydrogen and its thermal stability. Therefore, the effects of annealing and hydrogen plasma treatment on bulk ZnO (hydrothermally grown) were first studied. The use of bulk material for this purpose was motivated by the well-resolved photoluminescence (PL) lines observed for bulk ZnO, which allow the identification of the different lines related to hydrogen after plasma treatment. Annealing at 850 C was effective for the removal of most of the hydrogen related transitions in the near-band-edge emission. Also, additional transitions at ~3.364 eV and ~3.361 eV were observed after hydrogen plasma treatment, which were ascribed to hydrogen-Zn vacancy complexes. In this work, a comparative study of the annealing ambient and temperature on ZnO films grown on GaAs substrate, using diethyl zinc (DEZn) and tertiary butanol (TBOH), showed that arsenic diffuses in the ZnO films and gives a shallow level in the band gap, which is involved in an acceptor-bound exciton line at 3.35 eV. This shallow level is visible when annealing is performed in oxygen, but not when annealing is performed in nitrogen, and indeed only for annealing temperatures around 550 C. However, annealing in either ambient also causes zinc to diffuse from the ZnO films into the GaAs substrate, rendering the electrical properties deduced from Hall measurements ambiguous. For ZnO:N, NO was used as both oxygen and nitrogen sources. Monitoring the concentration of nitrogen, carbon and hydrogen in the ZnO films, the formation of different complexes from these impurities were deduced. Furthermore, an investigation of the effect of annealing on the concentrations of impurities showed that their out- diffusion was strongly dependent on the crystalline quality of the ZnO films. For porous ZnO films, obtained at low growth temperatures (≤310 C), the out-diffusion of impurities was efficient, whereas for films grown at higher temperatures, which have improved crystalline quality, the out-diffusion was practically nonexistent. The out-diffusion of unwanted impurities may activate the nitrogen dopant in the ZnO films, as was confirmed by the PL measurements on the different samples grown at different temperatures. PL transitions at ~3.24 eV and ~3.17 eV were related to substitutional NO. These transitions were more dominant in the spectra of samples grown at low temperatures. An additional transition at ~3.1 eV was assigned to a donor-acceptor pair transition involving VZn, instead of NO, as previously reported.
- Full Text:
- Date Issued: 2010
- Authors: Dangbegnon, Julien Kouadio
- Date: 2010
- Subjects: Photoluminescence , Zinc oxide , Nitrogen , Arsenic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10518 , http://hdl.handle.net/10948/1216 , Photoluminescence , Zinc oxide , Nitrogen , Arsenic
- Description: In this work, the optical properties of ZnO doped with arsenic and nitrogen were studied. The ZnO samples were grown by Metalorganic Chemical Vapor Deposition (MOCVD). The solubility of nitrogen in the ZnO films, as well as its activation upon annealing, was also investigated. Hydrogen is known as a major source for passivation of the acceptors in ZnO:N. Therefore, it is crucial to dissociate the complex(es) formed by nitrogen and hydrogen and diffuse out the hydrogen in order to prevent the reformation of such complexes. High temperatures (≥ 600 C) are required for these purposes. In order to effectively remove the hydrogen impurities from the sample, it is important to know the optical fingerprints of hydrogen and its thermal stability. Therefore, the effects of annealing and hydrogen plasma treatment on bulk ZnO (hydrothermally grown) were first studied. The use of bulk material for this purpose was motivated by the well-resolved photoluminescence (PL) lines observed for bulk ZnO, which allow the identification of the different lines related to hydrogen after plasma treatment. Annealing at 850 C was effective for the removal of most of the hydrogen related transitions in the near-band-edge emission. Also, additional transitions at ~3.364 eV and ~3.361 eV were observed after hydrogen plasma treatment, which were ascribed to hydrogen-Zn vacancy complexes. In this work, a comparative study of the annealing ambient and temperature on ZnO films grown on GaAs substrate, using diethyl zinc (DEZn) and tertiary butanol (TBOH), showed that arsenic diffuses in the ZnO films and gives a shallow level in the band gap, which is involved in an acceptor-bound exciton line at 3.35 eV. This shallow level is visible when annealing is performed in oxygen, but not when annealing is performed in nitrogen, and indeed only for annealing temperatures around 550 C. However, annealing in either ambient also causes zinc to diffuse from the ZnO films into the GaAs substrate, rendering the electrical properties deduced from Hall measurements ambiguous. For ZnO:N, NO was used as both oxygen and nitrogen sources. Monitoring the concentration of nitrogen, carbon and hydrogen in the ZnO films, the formation of different complexes from these impurities were deduced. Furthermore, an investigation of the effect of annealing on the concentrations of impurities showed that their out- diffusion was strongly dependent on the crystalline quality of the ZnO films. For porous ZnO films, obtained at low growth temperatures (≤310 C), the out-diffusion of impurities was efficient, whereas for films grown at higher temperatures, which have improved crystalline quality, the out-diffusion was practically nonexistent. The out-diffusion of unwanted impurities may activate the nitrogen dopant in the ZnO films, as was confirmed by the PL measurements on the different samples grown at different temperatures. PL transitions at ~3.24 eV and ~3.17 eV were related to substitutional NO. These transitions were more dominant in the spectra of samples grown at low temperatures. An additional transition at ~3.1 eV was assigned to a donor-acceptor pair transition involving VZn, instead of NO, as previously reported.
- Full Text:
- Date Issued: 2010
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