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Title: Electron Mobility and Trapping in Ferrihydrite Nanoparticles

Abstract

Iron is the most abundant transition metal in the Earth’s crust, and naturally occurring iron oxide minerals play a commanding role in environmental redox reactions. Although iron oxide redox reactions are well-studied, their precise mechanisms are not fully understood. Recent work has shown that these involve electron transfer pathways within the solid, suggesting that overall reaction rates could be dependent upon electron mobility. Initial ultrafast spectroscopy studies of iron oxide nanoparticles sensitized by fluorescein derivatives supported a model for electron mobility based on polaronic hopping of electron charge carriers between iron sites, but the constitutive relationships between hopping mobilities and interfacial charge transfer processes has remained obscured. In this paper, we developed a coarse-grained lattice Monte Carlo model to simulate the collective mobilities and lifetimes of these photoinjected electrons with respect to recombination with adsorbed dye molecules for essential nanophase ferrihydrite and tested predictions made by the simulations using pump–probe spectroscopy. We acquired optical transient absorption spectra as a function of the particle size and under a variety of solution conditions and used cryogenic transmission electron microscopy to determine the aggregation state of the nanoparticles. We observed biphasic electron recombination kinetics over time scales that spanned from picoseconds to microseconds,more » the slower regime of which was fit with a stretched exponential decay function. The recombination rates were weakly affected by the nanoparticle size and aggregation state, suspension pH, and injection of multiple electrons per nanoparticle. Finally, we conclude that electron mobility indeed limits the rate of interfacial electron transfer in these systems, with the slowest processes relating to escape from deep traps, the presence of which outweighs the influence of environmental factors, such as pH-dependent surface charge.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5];  [6]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry; Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Division; Polish Academy of Sciences (PAS), Warsaw (Poland). Inst. of Physical Chemistry
  4. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Polish Academy of Sciences (PAS), Warsaw (Poland)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Science Foundation (NSF); The National Science Centre (NCN) (Poland)
OSTI Identifier:
1435087
Grant/Contract Number:
AC02-05CH11231; 0957696; DEC-2016/22/E/ST4/00446
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Earth and Space Chemistry
Additional Journal Information:
Journal Volume: 1; Journal Issue: 4; Journal ID: ISSN 2472-3452
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
charge separation; electron transfer; ferrihydrite; iron; redox

Citation Formats

Soltis, Jennifer A., Schwartzberg, Adam M., Zarzycki, Piotr, Penn, R. Lee, Rosso, Kevin M., and Gilbert, Benjamin. Electron Mobility and Trapping in Ferrihydrite Nanoparticles. United States: N. p., 2017. Web. doi:10.1021/acsearthspacechem.7b00030.
Soltis, Jennifer A., Schwartzberg, Adam M., Zarzycki, Piotr, Penn, R. Lee, Rosso, Kevin M., & Gilbert, Benjamin. Electron Mobility and Trapping in Ferrihydrite Nanoparticles. United States. doi:10.1021/acsearthspacechem.7b00030.
Soltis, Jennifer A., Schwartzberg, Adam M., Zarzycki, Piotr, Penn, R. Lee, Rosso, Kevin M., and Gilbert, Benjamin. Thu . "Electron Mobility and Trapping in Ferrihydrite Nanoparticles". United States. doi:10.1021/acsearthspacechem.7b00030.
@article{osti_1435087,
title = {Electron Mobility and Trapping in Ferrihydrite Nanoparticles},
author = {Soltis, Jennifer A. and Schwartzberg, Adam M. and Zarzycki, Piotr and Penn, R. Lee and Rosso, Kevin M. and Gilbert, Benjamin},
abstractNote = {Iron is the most abundant transition metal in the Earth’s crust, and naturally occurring iron oxide minerals play a commanding role in environmental redox reactions. Although iron oxide redox reactions are well-studied, their precise mechanisms are not fully understood. Recent work has shown that these involve electron transfer pathways within the solid, suggesting that overall reaction rates could be dependent upon electron mobility. Initial ultrafast spectroscopy studies of iron oxide nanoparticles sensitized by fluorescein derivatives supported a model for electron mobility based on polaronic hopping of electron charge carriers between iron sites, but the constitutive relationships between hopping mobilities and interfacial charge transfer processes has remained obscured. In this paper, we developed a coarse-grained lattice Monte Carlo model to simulate the collective mobilities and lifetimes of these photoinjected electrons with respect to recombination with adsorbed dye molecules for essential nanophase ferrihydrite and tested predictions made by the simulations using pump–probe spectroscopy. We acquired optical transient absorption spectra as a function of the particle size and under a variety of solution conditions and used cryogenic transmission electron microscopy to determine the aggregation state of the nanoparticles. We observed biphasic electron recombination kinetics over time scales that spanned from picoseconds to microseconds, the slower regime of which was fit with a stretched exponential decay function. The recombination rates were weakly affected by the nanoparticle size and aggregation state, suspension pH, and injection of multiple electrons per nanoparticle. Finally, we conclude that electron mobility indeed limits the rate of interfacial electron transfer in these systems, with the slowest processes relating to escape from deep traps, the presence of which outweighs the influence of environmental factors, such as pH-dependent surface charge.},
doi = {10.1021/acsearthspacechem.7b00030},
journal = {ACS Earth and Space Chemistry},
number = 4,
volume = 1,
place = {United States},
year = {Thu May 18 00:00:00 EDT 2017},
month = {Thu May 18 00:00:00 EDT 2017}
}

Journal Article:
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  • Iron is the most abundant transition metal in the Earth's crust, and naturally occurring iron oxide minerals play a commanding role in environmental redox reactions. Although iron oxide redox reactions are well studied, their precise mechanisms are not fully understood. Recent work has shown that these involve electron transfer pathways within the solid, suggesting that overall reaction rates could be dependent on electron mobility. Initial ultrafast spectroscopy studies of iron oxide nanoparticles sensitized by fluorescein derivatives supported a model for electron mobility based on polaronic hopping of electron charge carriers between iron sites, but the constitutive relationships between hopping mobilitiesmore » and interfacial charge transfer processes has remained obscured. We developed a coarse-grained lattice Monte Carlo model to simulate the collective mobilities and lifetimes of these photoinjected electrons with respect to recombination with adsorbed dye molecules for the essential nanophase ferrihydrite, and tested predictions made by the simulations using pump-probe spectroscopy. We acquired optical transient absorption spectra as a function of particle size and under a variety of solution conditions, and used cryogenic transmission electron microscopy to determine the aggregation state of the nanoparticles. We observed biphasic electron recombination kinetics over timescales that spanned picoseconds to microseconds, the slower regime of which was fit with a stretched exponential decay function. The recombination rates were weakly affected by nanoparticle size and aggregation state, suspension pH, and the injection of multiple electrons per nanoparticle. We conclude that electron mobility indeed limits the rate of interfacial electron transfer in these systems with the slowest processes relating to escape from deep traps, the presence of which outweighs the influence of environmental factors such as pH-dependent surface charge.« less
  • In this research, we assessed the abundance of point defects and their influence on the resistivity, the electron mobility-lifetime (μτ{sub e}) product, and the electron trapping time in CdTeSe crystals grown under different conditions using the traveling heater method. We used current-deep level transient spectroscopy to determine the traps' energy, their capture cross-section, and their concentration. Further, we used these data to determine the trapping and de-trapping times for the charge carriers. The data show that detectors with a lower concentration of In-dopant have a higher density of A-centers and Cd double vacancies (V{sub Cd}{sup - -}). The high concentrations ofmore » V{sub Cd}{sup - -} and A-centers, along with the deep trap at 0.86 eV and low density of 1.1 eV energy traps, are the major cause of the detectors' low resistivity, and most probably, a major contributor to the low μτ{sub e} product. Our results indicate that the energy levels of point defects in the bandgap, their concentrations, capture cross-sections, and their trapping and de-trapping times play an important role in the detector's performance, especially for devices that rely solely on electron transport.« less
  • Water-related redox couples in ambient air are identified as an important source of the surface trapping states, dynamic on-resistance, and drain current collapse in AlGaN/GaN high electron mobility transistors (HEMTs). Through in-situ X-ray photoelectron spectroscopy (XPS), direct signature of the water-related species—hydroxyl groups (OH) was found at the AlGaN surface at room temperature. It was also found that these species, as well as the current collapse, can be thermally removed above 200 °C in vacuum conditions. An electron trapping mechanism based on the H{sub 2}O/H{sub 2} and H{sub 2}O/O{sub 2} redox couples is proposed to explain the 0.5 eV energy level commonlymore » attributed to the surface trapping states. Finally, the role of silicon nitride passivation in successfully removing current collapse in these devices is explained by blocking the water molecules away from the AlGaN surface.« less
  • The influence of electric field (EF) on the dynamic ON-resistance (dyn-R{sub DS[ON]}) and threshold-voltage shift (ΔV{sub th}) of AlGaN/GaN high electron mobility transistors on Si has been investigated using pulsed current-voltage (I{sub DS}-V{sub DS}) and drain current (I{sub D}) transients. Different EF was realized with devices of different gate-drain spacing (L{sub gd}) under the same OFF-state stress. Under high-EF (L{sub gd} = 2 μm), the devices exhibited higher dyn-R{sub DS[ON]} degradation but a small ΔV{sub th} (∼120 mV). However, at low-EF (L{sub gd} = 5 μm), smaller dyn-R{sub DS[ON]} degradation but a larger ΔV{sub th} (∼380 mV) was observed. Our analysis shows that under OFF-state stress, the gatemore » electrons are injected and trapped in the AlGaN barrier by tunnelling-assisted Poole-Frenkel conduction mechanism. Under high-EF, trapping spreads towards the gate-drain access region of the AlGaN barrier causing dyn-R{sub DS[ON]} degradation, whereas under low-EF, trapping is mostly confined under the gate causing ΔV{sub th}. A trap with activation energy 0.33 eV was identified in the AlGaN barrier by I{sub D}-transient measurements. The influence of EF on trapping was also verified by Silvaco TCAD simulations.« less
  • Effects of residual C impurities and Ga vacancies on the dynamic instabilities of AlN/AlGaN/GaN metal insulator semiconductor high electron mobility transistors are investigated. Secondary ion mass spectroscopy, positron annihilation spectroscopy, and steady state and time-resolved photoluminescence (PL) measurements have been performed in conjunction with electrical characterization and current transient analyses. The correlation between yellow luminescence (YL), C- and Ga vacancy concentrations is investigated. Time-resolved PL indicating the C{sub N} O{sub N} complex as the main source of the YL, while Ga vacancies or related complexes with C seem not to play a major role. The device dynamic performance is foundmore » to be significantly dependent on the C concentration close to the channel of the transistor. Additionally, the magnitude of the YL is found to be in agreement with the threshold voltage shift and with the on-resistance degradation. Trap analysis of the GaN buffer shows an apparent activation energy of ∼0.8 eV for all samples, pointing to a common dominating trapping process and that the growth parameters affect solely the density of trap centres. It is inferred that the trapping process is likely to be directly related to C based defects.« less