Matching Items (6)
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- All Subjects: Electron paramagnetic resonance
- All Subjects: Pyrites
- Creators: Newman, Nathan
Description
A series of pyrite thin films were synthesized using a novel sequential evaporation
technique to study the effects of substrate temperature on deposition rate and micro-structure of
the deposited material. Pyrite was deposited in a monolayer-by-monolayer fashion using
sequential evaporation of Fe under high vacuum, followed by sulfidation at high S pressures
(typically > 1 mTorr to 1 Torr). Thin films were synthesized using two different growth processes; a
one-step process in which a constant growth temperature is maintained throughout growth, and a
three-step process in which an initial low temperature seed layer is deposited, followed by a high
temperature layer, and then finished with a low temperature capping layer. Analysis methods to
analyze the properties of the films included Glancing Angle X-Ray Diffraction (GAXRD),
Rutherford Back-scattering Spectroscopy (RBS), Transmission Electron Microscopy (TEM),
Secondary Ion Mass Spectroscopy (SIMS), 2-point IV measurements, and Hall effect
measurements. Our results show that crystallinity of the pyrite thin film improves and grain size
increases with increasing substrate temperature. The sticking coefficient of Fe was found to
increase with increasing growth temperature, indicating that the Fe incorporation into the growing
film is a thermally activated process.
technique to study the effects of substrate temperature on deposition rate and micro-structure of
the deposited material. Pyrite was deposited in a monolayer-by-monolayer fashion using
sequential evaporation of Fe under high vacuum, followed by sulfidation at high S pressures
(typically > 1 mTorr to 1 Torr). Thin films were synthesized using two different growth processes; a
one-step process in which a constant growth temperature is maintained throughout growth, and a
three-step process in which an initial low temperature seed layer is deposited, followed by a high
temperature layer, and then finished with a low temperature capping layer. Analysis methods to
analyze the properties of the films included Glancing Angle X-Ray Diffraction (GAXRD),
Rutherford Back-scattering Spectroscopy (RBS), Transmission Electron Microscopy (TEM),
Secondary Ion Mass Spectroscopy (SIMS), 2-point IV measurements, and Hall effect
measurements. Our results show that crystallinity of the pyrite thin film improves and grain size
increases with increasing substrate temperature. The sticking coefficient of Fe was found to
increase with increasing growth temperature, indicating that the Fe incorporation into the growing
film is a thermally activated process.
ContributorsWertheim, Alex (Author) / Newman, Nathan (Thesis advisor) / Singh, Rakesh (Committee member) / Bertoni, Mariana (Committee member) / Arizona State University (Publisher)
Created2014
Description
Pyrite is a 0.95 eV bandgap semiconductor which is purported to have great potential in widespread, low–cost photovoltaic cells. A thorough material selection process was used in the design of a pyrite sequential vapor deposition chamber aimed at reducing and possibly eliminating contamination during thin film growth. The design process focused on identifying materials that do not produce volatile components when exposed to high temperatures and high sulfur pressures. Once the materials were identified and design was completed, the ultra–high vacuum growth system was constructed and tested.
Pyrite thin films were deposited using the upgraded sequential vapor deposition chamber by varying the substrate temperature from 250°C to 420°C during deposition, keeping sulfur pressure constant at 1 Torr. Secondary Ion Mass Spectrometry (SIMS) results showed that all contaminants in the films were reduced in concentration by orders of magnitude from those grown with the previous system. Characterization techniques of Rutherford Back–scattering Spectrometry (RBS), X–Ray Diffraction (XRD), Raman Spectroscopy, Optical Profilometry and UV/Vis/Near–IR Spectroscopy were performed on the deposited thin films. The results indicate that stoichiometric ratio of S:Fe, structural–quality (epitaxy), optical roughness and percentage of pyrite in the deposited thin films improve with increase in deposition temperature. A Tauc plot of the optical measurements indicates that the pyrite thin films have a bandgap of 0.94 eV.
Pyrite thin films were deposited using the upgraded sequential vapor deposition chamber by varying the substrate temperature from 250°C to 420°C during deposition, keeping sulfur pressure constant at 1 Torr. Secondary Ion Mass Spectrometry (SIMS) results showed that all contaminants in the films were reduced in concentration by orders of magnitude from those grown with the previous system. Characterization techniques of Rutherford Back–scattering Spectrometry (RBS), X–Ray Diffraction (XRD), Raman Spectroscopy, Optical Profilometry and UV/Vis/Near–IR Spectroscopy were performed on the deposited thin films. The results indicate that stoichiometric ratio of S:Fe, structural–quality (epitaxy), optical roughness and percentage of pyrite in the deposited thin films improve with increase in deposition temperature. A Tauc plot of the optical measurements indicates that the pyrite thin films have a bandgap of 0.94 eV.
ContributorsWalimbe, Aditya (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry (Committee member) / Singh, Rakesh (Committee member) / Arizona State University (Publisher)
Created2016
Description
Measurements of the geometrical magnetoresistance of a conventional semiconductor, gallium arsenide (GaAs), and a more recently developed semiconductor, iron pyrite (FeS2) were measured in the Corbino disc geometry as a function of magnetic field to determine the carrier mobility (μm). These results were compared with measurements of the Hall mobility (μH) made in the Van der Pauw configuration. The scattering coefficient (ξ), defined as the ratio between magnetoresistance and Hall mobility (μm/μH), was determined experimentally for GaAs and natural pyrite from 300 K to 4.2 K. The effect of contact resistance and heating on the measurement accuracy is discussed.
ContributorsRavi, Aditya (Author) / Newman, Nathan (Thesis advisor) / Singh, Rakesh (Committee member) / Ferry, David K. (Committee member) / Arizona State University (Publisher)
Created2016
Description
Complex perovskite materials, including Ba(Zn1/3Ta2/3)O3 (BZT), are commonly used to make resonators and filters in communication systems because of their low dielectric loss and high-quality factors (Q). Transition metal additives are introduced (i.e., Ni2+, Co2+, Mn2+) to act as sintering agents and tune their temperature coefficient to zero or near-zero. However, losses in these commercial dielectric materials at cryogenic temperatures increase markedly due to spin-excitation resulting from the presence of paramagnetic defects. Applying a large magnetic field (e.g., 5 Tesla) quenches these losses and has allowed the study of other loss mechanisms present at low temperatures. Work was performed on Fe3+ doped LaAlO3. At high magnetic fields, the residual losses versus temperature plots exhibit Debye peaks at ~40 K, ~75 K, and ~215 K temperature and can be tentatively associated with defect reactions O_i^x+V_O^x→O_i^'+V_O^•, Fe_Al^x+V_Al^"→Fe_Al^'+V_Al^' and Al_i^x+Al_i^(••)→〖2Al〗_i^•, respectively. Peaks in the loss tangent versus temperature graph of Zn-deficient BZT indicate a higher concentration of defects and appear to result from conduction losses.Guided by the knowledge gained from this study, a systematic study to develop high-performance microwave materials for ultra-high performance at cryogenic temperatures was performed. To this end, the production and characterization of perovskite materials that were either undoped or contained non-paramagnetic additives were carried out. Synthesis of BZT ceramic with over 98% theoretical density was obtained using B2O3 or BaZrO3 additives. At 4 K, the highest Q x f product of 283,000 GHz was recorded for 5% BaZrO3 doped BZT.
A portable, inexpensive open-air spectrometer was designed, built, and tested to make the electron paramagnetic resonance (EPR) technique more accessible for high-school and university lab instruction. In this design, the sample is placed near a dielectric resonator and does not need to be enclosed in a cavity, as is used in commercial EPR spectrometers. Permanent magnets used produce fields up to 1500 G, enabling EPR measurements up to 3 GHz.
ContributorsGajare, Siddhesh Girish (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry (Committee member) / Tongay, Sefaattin (Committee member) / Chamberlin, Ralph (Committee member) / Arizona State University (Publisher)
Created2022
Description
Microwave properties of low-loss commercial dielectric materials are optimized by adding transition-metal dopants or alloying agents (i.e. Ni, Co, Mn) to tune the temperature coefficient of resonant frequency (τf) to zero. This occurs as a result of the temperature dependence of dielectric constant offsetting the thermal expansion. At cryogenic temperatures, the microwave loss in these dielectric materials is dominated by electron paramagnetic resonance (EPR) loss, which results from the spin-excitations of d-shell electron spins in exchange-coupled clusters. We show that the origin of the observed magnetically-induced shifts in the dielectric resonator frequency originates from the same mechanism, as described by the Kramers-Kronig relations. The temperature coefficient of resonator frequency, τf, is related to three material parameters according to the equation, τf = - (½ τε + ½ τµ + αL), where τε, τµ, and αL are the temperature coefficient of dielectric constant, magnetic permeability, and lattice constant, respectively. Each of these parameters for dielectric materials of interest are measured experimentally. These results, in combination with density functional simulations, developed a much improved understanding of the fundamental mechanisms responsible for τf. The same experimental methods have been used to characterize in-situ the physical nature and concentration of performance-degrading point defects in the dielectrics of superconducting planar microwave resonators.
ContributorsZhang, Shengke (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry L. (Committee member) / Chamberlin, Ralph (Committee member) / Flores, Marco (Committee member) / Singh, Rakesh K. (Committee member) / Arizona State University (Publisher)
Created2016
Description
Losses in commercial microwave dielectrics arise from spin excitations in paramagnetic transition metal dopants, at least at reduced temperatures. The magnitude of the loss tangent can be altered by orders of magnitude through the application of an external magnetic field. The goal of this thesis is to produce “smart” dielectrics that can be switched “on” or “off” at small magnetic fields while investigating the influence of transition metal dopants on the dielectric, magnetic, and structural properties.
A proof of principle demonstration of a resonator that can switch from a high-Q “on state” to a low-Q “off state” at reduced temperatures is demonstrated in (Al1-xFex)2O3 and La(Al1-xFex)O3. The Fe3+ ions are in a high spin state (S=5/2) and undergo electron paramagnetic resonance absorption transitions that increase the microwave loss of the system. Transitions occur between mJ states with a corresponding change in the angular momentum, J, by ±ħ (i.e., ΔmJ=±1) at small magnetic fields. The paramagnetic ions also have an influence on the dielectric and magnetic properties, which I explore in these systems along with another low loss complex perovskite material, Ca[(Al1-xFex)1/2Nb1/2]O3. I describe what constitutes an optimal microwave loss switchable material induced from EPR transitions and the mechanisms associated with the key properties.
As a first step to modeling the properties of high-performance microwave host lattices and ultimately their performance at microwave frequencies, a first-principles approach is used to determine the structural phase stability of various complex perovskites with a range of tolerance factors at 0 K and finite temperatures. By understanding the correct structural phases of these complex perovskites, the temperature coefficient of resonant frequency can be better predicted.
A strong understanding of these parameters is expected to open the possibility to produce new types of high-performance switchable filters, time domain MIMO’s, multiplexers, and demultiplexers.
A proof of principle demonstration of a resonator that can switch from a high-Q “on state” to a low-Q “off state” at reduced temperatures is demonstrated in (Al1-xFex)2O3 and La(Al1-xFex)O3. The Fe3+ ions are in a high spin state (S=5/2) and undergo electron paramagnetic resonance absorption transitions that increase the microwave loss of the system. Transitions occur between mJ states with a corresponding change in the angular momentum, J, by ±ħ (i.e., ΔmJ=±1) at small magnetic fields. The paramagnetic ions also have an influence on the dielectric and magnetic properties, which I explore in these systems along with another low loss complex perovskite material, Ca[(Al1-xFex)1/2Nb1/2]O3. I describe what constitutes an optimal microwave loss switchable material induced from EPR transitions and the mechanisms associated with the key properties.
As a first step to modeling the properties of high-performance microwave host lattices and ultimately their performance at microwave frequencies, a first-principles approach is used to determine the structural phase stability of various complex perovskites with a range of tolerance factors at 0 K and finite temperatures. By understanding the correct structural phases of these complex perovskites, the temperature coefficient of resonant frequency can be better predicted.
A strong understanding of these parameters is expected to open the possibility to produce new types of high-performance switchable filters, time domain MIMO’s, multiplexers, and demultiplexers.
ContributorsGonzales, Justin Michael (Author) / Newman, Nathan (Thesis advisor) / Muhich, Christopher (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2020