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- Genre: Doctoral Dissertation
Description
In this dissertation, I described my research on the growth and characterization of various nanostructures, such as nanowires, nanobelts and nanosheets, of different semiconductors in a Chemical Vapor Deposition (CVD) system.
In the first part of my research, I selected chalcogenides (such as CdS and CdSe) for a comprehensive study in growing two-segment axial nanowires and radial nanobelts/sheets using the ternary CdSxSe1-x alloys. I demonstrated simultaneous red (from CdSe-rich) and green (from CdS-rich) light emission from a single monolithic heterostructure with a maximum wavelength separation of 160 nm. I also demonstrated the first simultaneous two-color lasing from a single nanosheet heterostructure with a wavelength separation of 91 nm under sufficiently strong pumping power.
In the second part, I considered several combinations of source materials with different growth methods in order to extend the spectral coverage of previously demonstrated structures towards shorter wavelengths to achieve full-color emissions. I achieved this with the growth of multisegment heterostructure nanosheets (MSHNs), using ZnS and CdSe chalcogenides, via our novel growth method. By utilizing this method, I demonstrated the first growth of ZnCdSSe MSHNs with an overall lattice mismatch of 6.6%, emitting red, green and blue light simultaneously, in a single furnace run using a simple CVD system. The key to this growth method is the dual ion exchange process which converts nanosheets rich in CdSe to nanosheets rich in ZnS, demonstrated for the first time in this work. Tri-chromatic white light emission with different correlated color temperature values was achieved under different growth conditions. We demonstrated multicolor (191 nm total wavelength separation) laser from a single monolithic semiconductor nanostructure for the first time. Due to the difficulties associated with growing semiconductor materials of differing composition on a given substrate using traditional planar epitaxial technology, our nanostructures and growth method are very promising for various device applications, including but not limited to: illumination, multicolor displays, photodetectors, spectrometers and monolithic multicolor lasers.
In the first part of my research, I selected chalcogenides (such as CdS and CdSe) for a comprehensive study in growing two-segment axial nanowires and radial nanobelts/sheets using the ternary CdSxSe1-x alloys. I demonstrated simultaneous red (from CdSe-rich) and green (from CdS-rich) light emission from a single monolithic heterostructure with a maximum wavelength separation of 160 nm. I also demonstrated the first simultaneous two-color lasing from a single nanosheet heterostructure with a wavelength separation of 91 nm under sufficiently strong pumping power.
In the second part, I considered several combinations of source materials with different growth methods in order to extend the spectral coverage of previously demonstrated structures towards shorter wavelengths to achieve full-color emissions. I achieved this with the growth of multisegment heterostructure nanosheets (MSHNs), using ZnS and CdSe chalcogenides, via our novel growth method. By utilizing this method, I demonstrated the first growth of ZnCdSSe MSHNs with an overall lattice mismatch of 6.6%, emitting red, green and blue light simultaneously, in a single furnace run using a simple CVD system. The key to this growth method is the dual ion exchange process which converts nanosheets rich in CdSe to nanosheets rich in ZnS, demonstrated for the first time in this work. Tri-chromatic white light emission with different correlated color temperature values was achieved under different growth conditions. We demonstrated multicolor (191 nm total wavelength separation) laser from a single monolithic semiconductor nanostructure for the first time. Due to the difficulties associated with growing semiconductor materials of differing composition on a given substrate using traditional planar epitaxial technology, our nanostructures and growth method are very promising for various device applications, including but not limited to: illumination, multicolor displays, photodetectors, spectrometers and monolithic multicolor lasers.
ContributorsTurkdogan, Sunay (Author) / Ning, Cun Zheng (Thesis advisor) / Palais, Joseph C. (Committee member) / Yu, Hongbin (Committee member) / Mardinly, A. John (Committee member) / Arizona State University (Publisher)
Created2015
Description
Cubic boron nitride (c-BN), hexagonal boron nitride (h-BN), and semiconducting diamond all have physical properties that make them ideal materials for applications in high power and high frequency electronics, as well as radiation detectors. However, there is limited research on the unique properties and growth of c-BN or h-BN thin films. This dissertation addresses the deposition of c-BN via plasma enhanced chemical vapor deposition (PECVD) on boron doped diamond substrates. In-Situ X-ray photoelectron spectroscopy (XPS) is used to characterize the thickness and hexagonal to cubic ratio of boron nitride thin films. The effects of hydrogen concentration during the deposition of boron nitride are investigated. The boron nitride deposition rate is found to be dependent on the hydrogen gas flow. The sp2 to sp3 bonding is also found to be dependent on the hydrogen gas flow. Preferential growth of h-BN is observed when an excess of hydrogen is supplied to the reaction, while h-BN growth is suppressed when hydrogen flow is reduced to be the limiting reactant. Reduced hydrogen flow is also observed to promote preferential growth of c-BN.
The hydrogen limited reaction is used to deposit c-BN on single crystal (100) boron-doped diamond substrates. In-situ ultra-violet photoelectron spectroscopy (UPS) and XPS are used to deduce the valence band offset of the diamond/c-BN interface. A valence band offset of -0.3 eV is measured with the diamond VBM above the VBM of c-BN. This value is then discussed in context of previous experimental results and theoretical calculations.
Finally, UPS and XPS are used to characterize the surface states of phosphorus-doped diamond. Variations within the processing parameters for surface preparation and the effects on the electronic surface states are presented and discussed.
ContributorsBrown, Jesse (Author) / Nemanich, Robert J (Thesis advisor) / Alarcon, Ricardo (Committee member) / Lindsay, Stuart (Committee member) / Zaniewski, Anna (Committee member) / Arizona State University (Publisher)
Created2021
Description
Few-layer black phosphorous (FLBP) is one of the most important two-dimensional (2D) materials due to its strongly layer-dependent quantized bandstructure, which leads to wavelength-tunable optical and electrical properties. This thesis focuses on the preparation of stable, high-quality FLBP, the characterization of its optical properties, and device applications.Part I presents an approach to preparing high-quality, stable FLBP samples by combining O2 plasma etching, boron nitride (BN) sandwiching, and subsequent rapid thermal annealing (RTA). Such a strategy has successfully produced FLBP samples with a record-long lifetime, with 80% of photoluminescence (PL) intensity remaining after 7 months. The improved material quality of FLBP allows the establishment of a more definitive relationship between the layer number and PL energies.
Part II presents the study of oxygen incorporation in FLBP. The natural oxidation formed in the air environment is dominated by the formation of interstitial oxygen and dangling oxygen. By the real-time PL and Raman spectroscopy, it is found that continuous laser excitation breaks the bonds of interstitial oxygen, and free oxygen atoms can diffuse around or form dangling oxygen under low heat. RTA at 450 °C can turn the interstitial oxygen into dangling oxygen more thoroughly. Such oxygen-containing samples show similar optical properties to the pristine BP samples. The bandgap of such FLBP samples increases with the concentration of the incorporated oxygen.
Part III deals with the investigation of emission natures of the prepared samples. The power- and temperature-dependent measurements demonstrate that PL emissions are dominated by excitons and trions, with a combined percentage larger than 80% at room temperature. Such measurements allow the determination of trion and exciton binding energies of 2-, 3-, and 4-layer BP, with values around 33, 23, 15 meV for trions and 297, 276, 179 meV for excitons at 77K, respectively.
Part IV presents the initial exploration of device applications of such FLBP samples. The coupling between photonic crystal cavity (PCC) modes and FLBP's emission is realized by integrating the prepared sandwich structure onto 2D PCC. Electroluminescence has also been achieved by integrating such materials onto interdigital electrodes driven by alternating electric fields.
ContributorsLi, Dongying (Author) / Ning, Cun-Zheng (Thesis advisor) / Vasileska, Dragica (Committee member) / Lai, Ying-Cheng (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2022
Description
MAX phases are an intriguing class of materials with exotic combinations of properties, essentially turning them into metallic ceramics. Despite this unique feature, no commercialization has been accomplished yet. Looking at the state of the art within the MAX phase community, almost all published studies can be summarized using the term “traditional high temperature synthesis”. Contrasting the scientific interest that has been on the rise especially since the discovery of MXenes, the synthetic spectrum has been largely the same as it has been over the past decades.Herein, the newly-emerging sol-gel chemistry is being explored as an alternative non-conventional synthetic approach. Building on the successful sol-gel synthesis of Cr2GaC, this study focuses around the expansion of sol-gel chemistry for MAX phases. Starting with a thorough mechanistic investigation into the reaction pathway of sol-gel synthesized Cr2GaC, the chemical understanding of this system is drastically deepened. It is shown how the preliminary nano-structured metal-oxide species develop into bulk oxides, before the amorphous and disordered
graphite partakes in the reaction and reduces the metals into the MAX phase.
Furthermore, the technique is extended to the two Ge- based MAX phases V2GeC and Cr2GeC, a critical step needed to prove the viability and applicability of the newly developed technique. Additionally, by introducing Mn into the Cr-Ga-C system, a Mn-doping was achieved, and for the first time for (Cr1–xMnx)2GaC, a unit cell increase could be recorded. Based on magnetometry measurements, the currently widely accepted assumption of statistically distributed Mn in the M-layer is challenged.
The versatility of wet chemistry is explored using the model system Cr2GaC. Firstly, the MAX phase can be obtained in a microwire shape leveraging the branched biopolymer dextran, eliminating the need for any post-synthesis machining. Via halide intercalation, the electrical transport properties could be purposefully engineered.
Secondly, leveraging the unique and linear biopolymer chitosan, Cr2GaC was obtained as thick films and dense microspheres, drastically opening potential areas of application for MAX phases. Lastly, hollow microspheres with diameters of tens of μm were synthesized via carboxymethylated dextran. This shape once more opens the door to very specific applications requiring sophisticated structures.
ContributorsSiebert, Jan (Author) / Birkel, Christina (Thesis advisor) / Gould, Ian (Committee member) / Kouvetakis, John (Committee member) / Arizona State University (Publisher)
Created2022
Description
The mechanism of loss in high performance microwave dielectrics with complex perovskite structure, including Ba(Zn1/3Ta2/3)O3, Ba(Cd1/3Ta2/3)O3, ZrTiO4-ZnNb2O6, Ba(Zn1/3Nb2/3)O3, and BaTi4O9-BaZn2Ti4O11, has been investigated. We studied materials synthesized in our own lab and from commercial vendors. Then the measured loss tangent was correlated to the optical, structural, and electrical properties of the material. To accurately and quantitatively determine the microwave loss and Electron Paramagnetic Resonance (EPR) spectra as a function of temperature and magnetic field, we developed parallel plate resonator (PPR) and dielectric resonator (DR) techniques. Our studies found a marked increase in the loss at low temperatures is found in materials containing transition metal with unpaired d-electrons as a result of resonant spin excitations in isolated atoms (light doping) or exchange coupled clusters (moderate to high doping) ; a mechanism that differs from the usual suspects. The loss tangent can be drastically reduced by applying static magnetic fields. Our measurements also show that this mechanism significantly contributes to room temperature loss, but does not dominate. In order to study the electronic structure of these materials, we grew single crystal thin film dielectrics for spectroscopic studies, including angular resolved photoemission spectroscopy (ARPES) experiment. We have synthesized stoichiometric Ba(Cd1/3Ta2/3)O3 [BCT] (100) dielectric thin films on MgO (100) substrates using Pulsed Laser Deposition. Over 99% of the BCT film was found to be epitaxial when grown with an elevated substrate temperature of 635 C, an enhanced oxygen pressures of 53 Pa and a Cd-enriched BCT target with a 1 mol BCT: 1.5 mol CdO composition. Analysis of ultra violet optical absorption results indicate that BCT has a bandgap of 4.9 eV.
ContributorsLiu, Lingtao (Author) / Newman, Nathan (Thesis advisor) / Marzke, Robert (Committee member) / Chamberlin, Ralph (Committee member) / Arizona State University (Publisher)
Created2013
Description
This work systematically investigates structure-stability relations in various polymer derived ceramic (PDC) systems and metal organic frameworks (MOFs), both of which are hybrid materials. The investigation of silicon carbides (SiC) confirms thermodynamic stabilization of PDCs with increasing mixed bonding (Si bonded to both C, O and/or N). The study of more complex silicon oxycarbide (SiOC) structures shows stabilization of SiOCs with increasing pyrolysis temperature (between 1200 and1500 oC), and points to dissimilarities in the stabilizing effect of different mixed bonding environments (SiO3C, SiO2C2, or SiOC3) and their relative amounts. Analyses of quaternary silicon oxycarbonitride (SiC(N)(O)) materials suggests increased stabilization with increasing N content, and superior stabilization due to SiNxC4-x compared to SiOxC4-x mixed bonds. Investigation of the energetics of metal filler (Nb, Hf, Ta) incorporation in SiOCs shows that choice of metal filler influences the composition, structural evolution, and thermodynamic stability in PDCs. Ta fillers can stabilize otherwise unstable SiO3C mixed bonds. Independent of metal incorporation or lack thereof, in SiOC systems, higher pyrolysis temperature (1200-1500 oC) forms more stable ceramics. The stabilizing effect of order/disorder of the free carbon phase is system-dependent. The work on (MOFs) highlights stabilization trends obtained from the investigation of zeolitic imidazolate frameworks (ZIFs) and boron imidazolate frameworks (BIFs) based on azolate linkers. Study of the energetics of metal (Co(II), Cu (II), and Zn (II) ) substitution in isostructural ZIFs shows that in MOFs the stabilizing effect of metal is dependent on both framework topology (diamondoid (dia) > sodalite (SOD)) and dimensionality (2D > 3D). Thermodynamic analyses of metal substitution (Ag(I), Cu(I), and Li (I)) in isostructural ii SOD and dia BIF systems confirm increase in density as a general descriptor for increased stabilization in MOFs. The study of energetics of guest-host interactions during CO2 incorporation in azolate frameworks (i.e., ZIF-8) shows strong dependence of energetics of adsorption on choice of linker and metal. Additionally, several energetically favorable reaction pathways for the formation of CO3-ZIF-8 have been identified. Both PDCs and MOFs show a complex energetic landscape, with identifiable system dependent and general structural descriptors for increased thermodynamic stabilization and tunability of the energetics of guest-host interactions.
ContributorsLeonel, Gerson J (Author) / Navrotsky, Alexandra (Thesis advisor) / Dai, Lenore (Committee member) / Thomas, Mary (Committee member) / Singh, Gurpreet (Committee member) / Friščić, Tomislav (Committee member) / Arizona State University (Publisher)
Created2023
Description
The first part of this dissertation focuses on quantum structures with type-II band alignment, which are designed for applications in infrared photodetection and optical nonlinearity. A short- and mid-wavelength infrared dual-band optically-addressed photodetector structure has been designed and fabricated by molecular beam epitaxy, which is used to demonstrate the operational principles of optical address for extended tri-band detection. High-resolution x-ray diffraction and photoluminescence measurement were used to characterize the samples and revealed excellent crystalline quality and optical properties. An analytical model has been developed to address the effects of luminescence coupling and light leakage effects in optically-addressed tri-band photodetectors in terms of the absorber thicknesses and photoluminescence quantum efficiencies.Beyond superlattices, asymmetric quantum wells with type-II band alignment find application in optical nonlinearity enhancement which is the result of increased wavefunction overlap and larger electric dipole moments of the interband transitions compared to the conventional structures with type-I band edge alignment. The novel type-II AQW structure exhibits interband second-order susceptibility tensor elements ranging between 20 pm/V to 1.60×103 pm/V for nearly-resonant optical rectification and difference frequency generation applications at near-infrared and terahertz wavelengths, an improvement of nearly one order of magnitude over the type-I structures and one to three orders of magnitude over natural crystals such as LiNbO3, KTP, or GaAs. A factor of 2-3 further enhancement of the tensor elements is achieved by optimizing the well widths and band offsets of the type-II asymmetric quantum wells.
The second part of the dissertation reports the study of CdSe thin films with mixed zincblende and wurtzite phases grown on lattice-matched InAs(100) substrate using molecular beam epitaxy. These CdSe thin films reveal single-phase zincblende (ZB) structure with high crystalline quality with low defect density. In contrast, CdSe layers grown on lattice-matched InAs(111)B (As-terminated) substrates under different growth temperatures and Cd/Se flux ratios all have their demonstrated mixed ZB and wurtzite phases in coexistence confirmed by high-resolution x-ray diffraction, transmission electron microscopy and photoluminescence measurements. The reason for these properties is due to the small formation energy difference between the ZB and WZ phases of CdSe, which has been confirmed by density functional theory simulations.
ContributorsJu, Zheng (Author) / Zhang, Yong-Hang YHZ (Thesis advisor) / Smith, David DJS (Committee member) / Johnson, Shane SRJ (Committee member) / Ponce, Fernando FAP (Committee member) / Arizona State University (Publisher)
Created2023
Description
Air conditioning is a significant energy consumer in buildings, especially in humid regions where a substantial portion of energy is used to remove moisture rather than cool the air. Traditional dehumidification methods, which cool air to its dew point to condense water vapor, are energy intensive. This process unnecessarily overcools the air, only to reheat it to the desired temperature.This research introduces thermoresponsive materials as efficient desiccants to reduce energy demand for dehumidification. A system using lower critical solution temperature (LCST) type ionic liquids (ILs) as dehumidifiers is presented. Through the Flory-Huggins theory of mixtures, interactions between ionic liquids and water are analyzed. LCST ionic liquids demonstrate superior performance, with a coefficient of performance (COP) four times higher than non-thermoresponsive desiccants under similar conditions. The efficacy of ionic liquids as dehumidifiers is assessed based on properties like LCST temperature and enthalpic interaction parameter.
The research also delves into thermoresponsive solid desiccants, particularly polymers, using the Vrentas-Vrentas model. This model offers a more accurate depiction of their behaviors compared to the Flory-Huggins theory by considering elastic energy stored in the polymers. Moisture absorption in thin film polymers is studied under diverse conditions, producing absorption isotherms for various temperatures and humidities. Using temperature-dependent interaction parameters, the behavior of the widely-used thermoresponsive polymer (TRP) PNIPAAm and hypothetical TRPs is investigated. The parameters from the model are used as input to do a finite element analysis of a thermoresponsive dehumidifier. This model demonstrates the complete absorption-desorption cycle under varied conditions such as polymer absorption temperature, relative humidity, and air speed. Results indicate that a TRP with enhanced absorption capacity and an LCST of 50℃ achieves a peak moisture removal efficiency (MRE) of 0.9 at 75% relative humidity which is comparable to other existing thermoresponsive dehumidification systems. But other TRPs with even greater absorption capacity can produce MRE as high as 3.6. This system also uniquely recovers water in liquid form.
ContributorsRana, Ashish (Author) / Wang, Robert RW (Thesis advisor) / Green, Matthew MG (Committee member) / Milcarek, Ryan RM (Committee member) / Wang, Liping LW (Committee member) / Phelan, Patrick PP (Committee member) / Arizona State University (Publisher)
Created2023
The Intercoupling of Thermal Transport and Mechanical Properties in Colloidal Nanocrystal Assemblies
Description
Colloidal nanocrystals (NCs) are promising candidates for a wide range of applications (electronics, optoelectronics, photovoltaics, thermoelectrics, etc.). Mechanical and thermal transport property play very important roles in all of these applications. On one hand, mechanical robustness and high thermal conductivity are desired in electronics, optoelectronics, and photovoltaics. This improves thermomechanical stability and minimizes the temperature rise during the device operation. On the other hand, low thermal conductivity is desired for higher thermoelectric figure of merit (ZT). This dissertation demonstrates that ligand structure and nanocrystal ordering are the primary determining factors for thermal transport and mechanical properties in colloidal nanocrystal assemblies. To eliminate the mechanics and thermal transport barrier, I first propose a ligand crosslinking method to improve the thermal transport across the ligand-ligand interface and thus increasing the overall thermal conductivity of NC assemblies. Young’s modulus of nanocrystal solids also increases simultaneously upon ligand crosslinking. My thermal transport measurements show that the thermal conductivity of the iron oxide NC solids increases by a factor of 2-3 upon ligand crosslinking. Further, I demonstrate that, though with same composition, long-range ordered nanocrystal superlattices possess higher mechanical and thermal transport properties than disordered nanocrystal thin films. Experimental measurements along with theoretical modeling indicate that stronger ligand-ligand interaction in NC superlattice accounts for the improved mechanics and thermal transport. This suggests that NC/ligand arranging order also plays important roles in determining mechanics and thermal transport properties of NC assemblies. Lastly, I show that inorganic ligand functionalization could lead to tremendous mechanical enhancement (a factor of ~60) in NC solids. After ligand exchange and drying, the short inorganic Sn2S64- ligands dissociate into a few atomic layers of amorphous SnS2 at room temperature and interconnects the neighboring NCs. I observe a reverse Hall-Petch relation as the size of NC decreases. Both atomistic simulations and analytical phase mixture modeling identify the grain boundaries and their activities as the mechanic bottleneck.
ContributorsWang, Zhongyong (Author) / Wang, Robert RW (Thesis advisor) / Wang, Liping LW (Committee member) / Newman, Nathan NN (Committee member) / Arizona State University (Publisher)
Created2021
Description
Over the past few years, research into the use of doped diamond in electronics has seen an exponential growth. In the course of finding ways to reduce the contact resistivity, nanocarbon materials have been an interesting focus. In this work, the transfer length method (TLM) was used to investigate Ohmic contact properties using the tri-layer stack Ti/Pt/Au on nitrogen-doped n-type conducting nano-carbon (nanoC) layers grown on (100) diamond substrates. The nanocarbon material was characterized using Secondary Ion Mass Spectrometry (SIMS), Scanning electron Microscopy (SEM) X-ray diffraction (XRD), Raman scattering and Hall effect measurements to probe the materials characteristics. Room temperature electrical measurements were taken, and samples were annealed to observe changes in electrical conductivity. Low specific contact resistivity values of 8 x 10^-5 Ωcm^2 were achieved, which was almost two orders of magnitude lower than previously reported values. The results were attributed to the increased nitrogen incorporation, and the presence of electrically active defects which leads to an increase in conduction in the nanocarbon. Further a study of light phosphorus doped layers using similar methods with Ti/Pt/Au contacts again yielded a low contact resistivity of about 9.88 x 10^-2 Ωcm^2 which is an interesting prospect among lightly doped diamond films for applications in devices such as transistors. In addition, for the first time, hafnium was substituted for Ti in the contact stack (Hf/Pt/Au) and studied on nitrogen doped nanocarbon films, which resulted in low contact resistivity values on the order of 10^-2 Ωcm^2. The implications of the results were discussed, and recommendations for improving the experimental process was outlined. Lastly, a method for the selective area growth of nanocarbon was developed and studied and the results provided an insight into how different characterizations can be used to confirm the presence of the nanocrystalline diamond material, the limitations due to the film thickness was explored and ideas for future work was proposed.
ContributorsAmonoo, Evangeline Abena (Author) / Thornton, Trevor (Thesis advisor) / Alford, Terry L (Thesis advisor) / Anwar, Shahriar (Committee member) / Theodore, David (Committee member) / Arizona State University (Publisher)
Created2023