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- Creators: Alford, Terry
- Resource Type: Text
Description
ABSTRACT
Autonomous smart windows may be integrated with a stack of active components, such as electrochromic devices, to modulate the opacity/transparency by an applied voltage. Here, we describe the processing and performance of two classes of visibly-transparent photovoltaic materials, namely inorganic (ZnO thin film) and fully organic (PCDTBT:PC70BM), for integration with electrochromic stacks.
Sputtered ZnO (2% Mn) films on ITO, with transparency in the visible range, were used to fabricate metal-semiconductor (MS), metal-insulator-semiconductor (MIS), and p-i-n heterojunction devices, and their photovoltaic conversion under ultraviolet (UV) illumination was evaluated with and without oxygen plasma-treated surface electrodes (Au, Ag, Al, and Ti/Ag). The MS Schottky parameters were fitted against the generalized Bardeen model to obtain the density of interface states (Dit ≈ 8.0×1011 eV−1cm−2) and neutral level (Eo ≈ -5.2 eV). These devices exhibited photoconductive behavior at λ = 365 nm, and low-noise Ag-ZnO detectors exhibited responsivity (R) and photoconductive gain (G) of 1.93×10−4 A/W and 6.57×10−4, respectively. Confirmed via matched-pair analysis, post-metallization, oxygen plasma treatment of Ag and Ti/Ag electrodes resulted in increased Schottky barrier heights, which maximized with a 2 nm SiO2 electron blocking layer (EBL), coupled with the suppression of recombination at the metal/semiconductor interface and blocking of majority carriers. For interdigitated devices under monochromatic UV-C illumination, the open-circuit voltage (Voc) was 1.2 V and short circuit current density (Jsc), due to minority carrier tunneling, was 0.68 mA/cm2.
A fully organic bulk heterojunction photovoltaic device, composed of poly[N-9’-heptadecanyl-2,7-carbazole-alt-5,5-(4’,7’-di-2-thienyli2’,1’,3’-benzothiadiazole)]:phenyl-C71-butyric-acidmethyl (PCDTBT:PC70BM), with corresponding electron and hole transport layers, i.e., LiF with Al contact and conducting
on-conducting (nc) PEDOT:PSS (with ITO/PET or Ag nanowire/PDMS contacts; the illuminating side), respectively, was developed. The PCDTBT/PC70BM/PEDOT:PSS(nc)/ITO/PET stack exhibited the highest performance: power conversion efficiency (PCE) ≈ 3%, Voc = 0.9V, and Jsc ≈ 10-15 mA/cm2. These stacks exhibited high visible range transparency, and provided the requisite power for a switchable electrochromic stack having an inkjet-printed, optically-active layer of tungsten trioxide (WO3), peroxo-tungstic acid dihydrate, and titania (TiO2) nano-particle-based blend. The electrochromic stacks (i.e., PET/ITO/LiClO4/WO3 on ITO/PET and Ag nanowire/PDMS substrates) exhibited optical switching under external bias from the PV stack (or an electrical outlet), with 7 s coloration time, 8 s bleaching time, and 0.36-0.75 optical modulation at λ = 525 nm. The devices were paired using an Internet of Things controller that enabled wireless switching.
Autonomous smart windows may be integrated with a stack of active components, such as electrochromic devices, to modulate the opacity/transparency by an applied voltage. Here, we describe the processing and performance of two classes of visibly-transparent photovoltaic materials, namely inorganic (ZnO thin film) and fully organic (PCDTBT:PC70BM), for integration with electrochromic stacks.
Sputtered ZnO (2% Mn) films on ITO, with transparency in the visible range, were used to fabricate metal-semiconductor (MS), metal-insulator-semiconductor (MIS), and p-i-n heterojunction devices, and their photovoltaic conversion under ultraviolet (UV) illumination was evaluated with and without oxygen plasma-treated surface electrodes (Au, Ag, Al, and Ti/Ag). The MS Schottky parameters were fitted against the generalized Bardeen model to obtain the density of interface states (Dit ≈ 8.0×1011 eV−1cm−2) and neutral level (Eo ≈ -5.2 eV). These devices exhibited photoconductive behavior at λ = 365 nm, and low-noise Ag-ZnO detectors exhibited responsivity (R) and photoconductive gain (G) of 1.93×10−4 A/W and 6.57×10−4, respectively. Confirmed via matched-pair analysis, post-metallization, oxygen plasma treatment of Ag and Ti/Ag electrodes resulted in increased Schottky barrier heights, which maximized with a 2 nm SiO2 electron blocking layer (EBL), coupled with the suppression of recombination at the metal/semiconductor interface and blocking of majority carriers. For interdigitated devices under monochromatic UV-C illumination, the open-circuit voltage (Voc) was 1.2 V and short circuit current density (Jsc), due to minority carrier tunneling, was 0.68 mA/cm2.
A fully organic bulk heterojunction photovoltaic device, composed of poly[N-9’-heptadecanyl-2,7-carbazole-alt-5,5-(4’,7’-di-2-thienyli2’,1’,3’-benzothiadiazole)]:phenyl-C71-butyric-acidmethyl (PCDTBT:PC70BM), with corresponding electron and hole transport layers, i.e., LiF with Al contact and conducting
on-conducting (nc) PEDOT:PSS (with ITO/PET or Ag nanowire/PDMS contacts; the illuminating side), respectively, was developed. The PCDTBT/PC70BM/PEDOT:PSS(nc)/ITO/PET stack exhibited the highest performance: power conversion efficiency (PCE) ≈ 3%, Voc = 0.9V, and Jsc ≈ 10-15 mA/cm2. These stacks exhibited high visible range transparency, and provided the requisite power for a switchable electrochromic stack having an inkjet-printed, optically-active layer of tungsten trioxide (WO3), peroxo-tungstic acid dihydrate, and titania (TiO2) nano-particle-based blend. The electrochromic stacks (i.e., PET/ITO/LiClO4/WO3 on ITO/PET and Ag nanowire/PDMS substrates) exhibited optical switching under external bias from the PV stack (or an electrical outlet), with 7 s coloration time, 8 s bleaching time, and 0.36-0.75 optical modulation at λ = 525 nm. The devices were paired using an Internet of Things controller that enabled wireless switching.
ContributorsAzhar, Ebraheem (Author) / Yu, Hongbin (Thesis advisor) / Dey, Sandwip (Thesis advisor) / Goryll, Michael (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2018
Description
Chemical Vapor Deposition (CVD) is the most widely used method to grow large-scale single layer graphene. However, a systematic experimental study of the relationship between growth parameters and graphene film morphology, especially in the industrially preferred cold wall CVD, has not been undertaken previously. This research endeavored to address this and provide comprehensive insight into the growth physics of graphene on supported solid and liquid Cu films using cold wall CVD.
A multi-chamber UHV system was customized and transformed into a cold wall CVD system to perform experiments. The versatile growth process was completely custom-automated by controlling the process parameters with LabVIEW. Graphene growth was explored on solid electrodeposited, recrystallized and thin sputter deposited Cu films as well as on liquid Cu supported on W/Mo refractory substrates under ambient pressure using Ar, H₂ and CH₄ mixtures.
The results indicate that graphene grown on Cu films using cold wall CVD follows a classical two-dimensional nucleation and growth mechanism. The nucleation density decreases and average size of graphene crystallites increases with increasing dilution of the CH₄/H₂ mixture by Ar, decrease in total flow rate and decrease in CH₄:H₂ ratio at a fixed substrate temperature and chamber pressure. Thus, the resulting morphological changes correspond with those that would be expected if the precursor deposition rate was varied at a fixed substrate temperature for physical deposition using thermal evaporation. The evolution of graphene crystallite boundary morphology with decreasing effective C deposition rate indicates the effect of edge diffusion of C atoms along the crystallite boundaries, in addition to H₂ etching, on graphene crystallite shape.
The roles of temperature gradient, chamber pressure and rapid thermal heating in C precursor-rich environment on graphene growth morphology on thin sputtered Cu films were explained. The growth mechanisms of graphene on substrates annealed under reducing and non-reducing environment were explained from the scaling functions of graphene island size distribution in the pre-coalescence regime. It is anticipated that applying the pre-coalescence size distribution method presented in this work to other 2D material systems may be useful for elucidating atomistic mechanisms of film growth that are otherwise difficult to obtain.
A multi-chamber UHV system was customized and transformed into a cold wall CVD system to perform experiments. The versatile growth process was completely custom-automated by controlling the process parameters with LabVIEW. Graphene growth was explored on solid electrodeposited, recrystallized and thin sputter deposited Cu films as well as on liquid Cu supported on W/Mo refractory substrates under ambient pressure using Ar, H₂ and CH₄ mixtures.
The results indicate that graphene grown on Cu films using cold wall CVD follows a classical two-dimensional nucleation and growth mechanism. The nucleation density decreases and average size of graphene crystallites increases with increasing dilution of the CH₄/H₂ mixture by Ar, decrease in total flow rate and decrease in CH₄:H₂ ratio at a fixed substrate temperature and chamber pressure. Thus, the resulting morphological changes correspond with those that would be expected if the precursor deposition rate was varied at a fixed substrate temperature for physical deposition using thermal evaporation. The evolution of graphene crystallite boundary morphology with decreasing effective C deposition rate indicates the effect of edge diffusion of C atoms along the crystallite boundaries, in addition to H₂ etching, on graphene crystallite shape.
The roles of temperature gradient, chamber pressure and rapid thermal heating in C precursor-rich environment on graphene growth morphology on thin sputtered Cu films were explained. The growth mechanisms of graphene on substrates annealed under reducing and non-reducing environment were explained from the scaling functions of graphene island size distribution in the pre-coalescence regime. It is anticipated that applying the pre-coalescence size distribution method presented in this work to other 2D material systems may be useful for elucidating atomistic mechanisms of film growth that are otherwise difficult to obtain.
ContributorsDas, Shantanu, Ph.D (Author) / Drucker, Jeff (Thesis advisor) / Alford, Terry (Committee member) / Chen, Tingyong (Committee member) / Arizona State University (Publisher)
Created2018
Description
Metal-organic frameworks (MOFs) are a new set of porous materials comprised of metals or metal clusters bonded together in a coordination system by organic linkers. They are becoming popular for gas separations due to their abilities to be tailored toward specific applications. Zirconium MOFs in particular are known for their high stability under standard temperature and pressure due to the strength of the Zirconium-Oxygen coordination bond. However, the acid modulator needed to ensure long range order of the product also prevents complete linker deprotonation. This leads to a powder product that cannot easily be incorporated into continuous MOF membranes. This study therefore implemented a new bi-phase synthesis technique with a deprotonating agent to achieve intergrowth in UiO-66 membranes. Crystal intergrowth will allow for effective gas separations and future permeation testing. During experimentation, successful intergrown UiO-66 membranes were synthesized and characterized. The degree of intergrowth and crystal orientations varied with changing deprotonating agent concentration, modulator concentration, and ligand:modulator ratios. Further studies will focus on achieving the same results on porous substrates.
ContributorsClose, Emily Charlotte (Author) / Mu, Bin (Thesis director) / Shan, Bohan (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
Description
ABSTRACT
Large-pore metal-organic framework (MOF) membranes offer potential in a number of gas and liquid separations due to their wide and selective adsorption capacities. A key characteristic of a number of MOF and zeolitic imidazolate framework (ZIF) membranes is their highly selective adsorption capacities for CO2. These membranes offer very tangible potential to separate CO2 in a wide array of industrially relevant separation processes, such as the separation from CO2 in flue gas emissions, as well as the sweetening of methane.
By virtue of this, the purpose of this dissertation is to synthesize and characterize two linear large-pore MOF membranes, MOF-5 and ZIF-68, and to study their gas separation properties in binary mixtures of CO¬2/N2 and CO2/CH4. The three main objectives researched are as follows. The first is to study the pervaporation behavior and stability of MOF-5; this is imperative because although MOF-5 exhibits desirable adsorption and separation characteristics, it is very unstable in atmospheric conditions. In determining its stability and behavior in pervaporation, this material can be utilized in conditions wherein atmospheric levels of moisture can be avoided. The second objective is to synthesize, optimize and characterize a linear, more stable MOF membrane, ZIF-68. The final objective is to study in tandem the high-pressure gas separation behavior of MOF-5 and ZIF-68 in binary gas systems of both CO2/N2 and CO2/CH4.
Continuous ZIF-68 membranes were synthesized via the reactive seeding method and the modified reactive seeding method. These membranes, as with the MOF-5 membranes synthesized herein, both showed adherence to Knudsen diffusion, indicating limited defects. Organic solvent experiments indicated that MOF-5 and ZIF-68 were stable in a variety of organic solvents, but both showed reductions in permeation flux of the tested molecules. These reductions were attributed to fouling and found to be cumulative up until a saturation of available bonding sites for molecules was reached and stable pervaporation permeances were reached for both. Gas separation behavior for MOF-5 showed direct dependence on the CO2 partial pressure and the overall feed pressure, while ZIF-68 did not show similar behavior. Differences in separation behavior are attributable to orientation of the ZIF-68 membranes.
Large-pore metal-organic framework (MOF) membranes offer potential in a number of gas and liquid separations due to their wide and selective adsorption capacities. A key characteristic of a number of MOF and zeolitic imidazolate framework (ZIF) membranes is their highly selective adsorption capacities for CO2. These membranes offer very tangible potential to separate CO2 in a wide array of industrially relevant separation processes, such as the separation from CO2 in flue gas emissions, as well as the sweetening of methane.
By virtue of this, the purpose of this dissertation is to synthesize and characterize two linear large-pore MOF membranes, MOF-5 and ZIF-68, and to study their gas separation properties in binary mixtures of CO¬2/N2 and CO2/CH4. The three main objectives researched are as follows. The first is to study the pervaporation behavior and stability of MOF-5; this is imperative because although MOF-5 exhibits desirable adsorption and separation characteristics, it is very unstable in atmospheric conditions. In determining its stability and behavior in pervaporation, this material can be utilized in conditions wherein atmospheric levels of moisture can be avoided. The second objective is to synthesize, optimize and characterize a linear, more stable MOF membrane, ZIF-68. The final objective is to study in tandem the high-pressure gas separation behavior of MOF-5 and ZIF-68 in binary gas systems of both CO2/N2 and CO2/CH4.
Continuous ZIF-68 membranes were synthesized via the reactive seeding method and the modified reactive seeding method. These membranes, as with the MOF-5 membranes synthesized herein, both showed adherence to Knudsen diffusion, indicating limited defects. Organic solvent experiments indicated that MOF-5 and ZIF-68 were stable in a variety of organic solvents, but both showed reductions in permeation flux of the tested molecules. These reductions were attributed to fouling and found to be cumulative up until a saturation of available bonding sites for molecules was reached and stable pervaporation permeances were reached for both. Gas separation behavior for MOF-5 showed direct dependence on the CO2 partial pressure and the overall feed pressure, while ZIF-68 did not show similar behavior. Differences in separation behavior are attributable to orientation of the ZIF-68 membranes.
ContributorsKasik, Alexandra Marie (Author) / Lin, Jerry (Thesis advisor) / Tasooji, Amaneh (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2015
Description
Nanocrystalline (NC) materials are of great interest to researchers due to their multitude of properties such as exceptional strength and radiation resistance owing to their high fraction of grain boundaries that act as defect sinks for radiation-induced defects, provided they are microstructurally stable. In this dissertation, radiation effects in microstructurally stable bulk NC copper (Cu)- tantalum (Ta) alloys engineered with uniformly dispersed Ta nano-precipitates are systematically probed. Towards this, both ex-situ and in-situ irradiations using heavy (self) ion, helium ion, and concurrent dual ion beams (He+Au) followed by isochronal annealing inside TEM were utilized to understand radiation tolerance and underlying mechanisms of microstructure evolution in stable NC alloys. With systematic self-ion irradiation, the high density of tantalum nanoclusters in Cu-10at.%Ta were observed to act as stable sinks in suppressing radiation hardening, in addition to stabilizing the grain boundaries; while the large incoherent precipitates experienced ballistic mixing and dissolution at high doses. Interestingly, the alloy exhibited a microstructure self-healing mechanism, where with a moderate thermal input, this dissolved tantalum eventually re-precipitated, thus replenishing the sink density. The high stability of these tantalum nanoclusters is attributed to the high positive enthalpy of mixing of tantalum in copper which also acted as a critical driving force against atomic mixing to facilitate re-precipitation of tantalum nanoclusters. Furthermore, these nanoclusters proved to be effective trapping sites for helium, thus sequestering helium into isolated small bubbles and aid in increasing the overall swelling threshold of the alloy. The alloy was then compositionally optimized to reduce the density of large incoherent precipitates without compromising on the grain size and nanocluster density (Cu-3at.%Ta) which resulted in a consistent and more promising response to high dose self-ion irradiation. In-situ helium and dual beam irradiation coupled with isochronal annealing till 723 K, also revealed a comparable microstructural stability and enhanced ability of Cu-3Ta in controlling bubble growth and suppressing swelling compared to Cu-10Ta indicating a promising improvement in radiation tolerance in the optimized composition. Overall, this work helps advancing the current understanding of radiation tolerance in stable nanocrystalline alloys and aid developing design strategies for engineering radiation tolerant materials with stable interfaces.
ContributorsSrinivasan, Soundarya (Author) / Solanki, Kiran (Thesis advisor) / Peralta, Pedro (Committee member) / Alford, Terry (Committee member) / Darling, Kristopher (Committee member) / Arizona State University (Publisher)
Created2021