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Interactions between ions and itinerant charges govern electronic processes ranging from the redox chemistry of molecules to the conductivity of organic semiconductors, but remain an open frontier in the study of microporous materials.
Experimental studies of electron transport through an edge-fused porphyrin oligomer in a graphene junction are interpreted within a Hubbard dimer framework.
Conformational control of π-conjugated molecules using intramolecular noncovalent bonds represents a promising strategy to tailor the solid-state molecular packing and electronic properties of these materials. Here, we report the design and synthesis of two model compounds featuring intramolecular hydrogen bonds formed between a center diazaisoindigo unit (the acceptor) and flanking indole units (the donor). Computational and experimental investigations show that these hydrogen bonds enthalpically stabilize the coplanar molecular conformation by over 10 kcal/mol. The formation of these hydrogen bonds is also slightly favorable in terms of entropy, ensuring high temperature stability of the planar conformation. In this work, thermal annealing of thin films of these compounds imparts high crystallinity and orientation in the solid state, while the non-hydrogen bond control only gave an amorphous solid. Field-effect transistor devices fabricated from these thin films exhibit hole mobilities up to 0.270 cm 2 V -1 s -1 , in contrast to the lack of measurable charge carrier mobility for the non-hydrogen bond control. This work demonstrates an efficient synthetic strategy to incorporate robust intramolecular hydrogen bonds into conjugated π-systems and elucidates the mechanism on how such hydrogen bonds promote the desired molecular conformation, solid-state packing, and electronic performances of conjugated organic materials.
Advances in the growth processes of 4H-SiC epitaxial layers have led to the continued expansion of epilayer thickness, allowing for the detection of more penetrative radioactive particles. In this work, we report the fabrication and characterization of high-resolution Schottky barrier radiation detectors on 250 μm thick n-type 4H-SiC epitaxial layers, the highest reported thickness to date. Several 8 × 8 mm 2 detectors were fabricated from a diced 100 mm diameter 4H-SiC epitaxial wafer grown on a conductive 4H-SiC substrate with a mean micropipe density of 0.11 cm -2 From the Mott–Schottky plots, the effective doping concentration was found to be in the range (0.95–1.85) × 10 14 cm -3 , implying that full depletion could be achieved at ~5.7 kV (0.5 MV/cm at the interface). The current-voltage characteristics demonstrated consistently low leakage current densities of 1–3 nA/cm 2 at a reverse bias of -800 V. This resulted in the pulse-height spectra generated using a 241Am alpha source (5486 keV) manifesting an energy resolution of less than 0.5% full width at half maximum (FWHM) for all the detectors at -200 V. The charge collection efficiencies (CCEs) were measured to be 98–99% with no discernable correlation to the energy resolution. A drift-diffusion model fit to the variation of CCE as a function of bias voltage, revealed a minority carrier diffusion length of ~10 μm. Deep level transient spectroscopy measurements on the best resolution detector revealed that the excellent performance was the result of having ultralow concentrations of the order of 1011 cm-3 lifetime limiting defects—Z 1/2 and EH 6/7 .
The dynamic nature of the metal halide perovskite lattice upon photoexcitation plays a vital role in their properties. Here we report an observation of light-induced structure dynamics in quasi-2D Ruddlesden–Popper phase perovskite thin films and its impact on the carrier transport properties. By a time-resolved X-ray scattering technique, we observe a rapid lattice expansion upon photoexcitation, followed by a slow relaxation over the course of 100 ns in the dark. Theoretical modeling suggests that the expansion originates from the lattice’s thermal fluctuations caused by photon energy deposition. Power dependent optical spectroscopy and photoconductivity indicate that high laser powers triggered a strong local structural disorder, which increased the charge dissociation activation energy that results in localized transport. Finally, our study investigates the impact of laser energy deposition on the lattices and the subsequent carrier transport properties, that are relevant to device operations.
Computer simulations of processes which control the relative abundances of ions in the trapping regions of geospace are compared with observations from discriminating ion detectors. Energy losses due to Coulomb collisions between ions and exospheric neutrals are considered, along with charge exchange losses and internal charge exchanges. The time evolution of energetic ion fluxes of equatorially mirroring ions under radial diffusion is modelled to include geomagnetic and geoelectric fluctutations. Limits to the validity of diffusion transport theory are discussed, and the simulation is noted to contain provisions for six ionic charge states and the source effect on the radiation belt oxygen ion distributions. Comparisons are made with ion flux data gathered on Explorer 45 and ISEE-1 spacecraft and results indicate that internal charge exchanges cause the radiation belt ion charge state to be independent of source charge rate characteristics, and relative charge state distribution is independent of the radially diffusive transport rate below the charge state redistribution zone.
Improvements in the charge storage properties of α-MoO 3 used as an electrode with a 30m ZnCl 2 water-in-salt electrolyte have been achieved by enhancements in electron and ion transport enabled by an inventive synthesis route. Electron transport was improved through the integration of MoO 3 with dopamine-derived carbon via a chemical preintercalation route, and enhanced ion transport was achieved by incorporating oxygen vacancies in MoO 3 structure through ethanol 2 reduction under hydrothermal conditions. Here, the presence of carbon was confirmed by corresponding D and G bands observed in Raman spectroscopy measurements. The presence of oxygen vacancies was proven through correlated XPS, TGA, Raman spectroscopy and XRD analyses, with the introduction of oxygen vacancies leading to an expanded interlayer region. Four-point probe measurements provided evidence of increased electronic conductivity due to the incorporation of carbon, and cyclic voltammetry-based charge storage mechanism analyses revealed increases in ion transport kinetics due to oxygen vacancy formation. Tuning the oxygen vacancy concentration is critical, as excessive concentrations of these point defects leads to structural instability and poor capacity retention. This work demonstrates the combined potential of carbon and oxygen vacancies in moderate concentrations to enhance the charge storage properties of transition metal oxides. The strategies developed in this study offer a path to the development of promising materials for high-rate, high-capacity, and long-duration electrochemical energy storage technologies.
It is of fundamental interest to understand the carrier of conserved quantum charges within protons and nuclei at high energy. Preliminary data from isobar collisions at RHIC reveal a scaled net-baryon to net-electric charge ratio (B/ΔQ × ΔZ/A) at midrapidity between 1.2 and 2, consistent with string junction model predictions. Here, we compute the initial stage scaled net baryon to net-electric charge ratio for isobar collisions. Our model incorporates a realization of the string junction model and models the nuclear structure. Our predictions identify the baseline expectations for such measurement and quantify the impact of the nuclear structure.
Conjugated polymers (CPs) with polar side chains can conduct electronic and ionic charges simultaneously, making them promising for bioelectronics, electrocatalysis and energy storage. Recent work showed that adding alkyl spacers between CP backbones and polar side chains improved electronic charge carrier mobility, reduced swelling and enhanced stability, without compromising ion transport. However, how alkyl spacers impact polymer backbone conformation and, subsequently, electronic properties remain unclear. In this work, we design two oxy-bithiophene-based CP series, each featuring progressively extended alkyl spacer lengths and two distinct molecular weight (MW) distributions. Using operando characterisations, we evaluate the (spectro)electrochemical and swelling properties of the polymer thin films, and their performance in organic field-effect transistors and organic electrochemical transistors. Surprisingly, alkyl spacers negatively impact the hole mobility of our polymers, with higher MW amplifying this effect. Using molecular dynamics simulations, we show that it is thermodynamically favourable for adjacent non-polar alkyl spacers to aggregate in polar electrolytes, leading to backbone twisting. Further spectroscopic measurements corroborate this prediction. Our findings demonstrate the active interactions between side chain structure, MW and electrolyte/solvent polarity in influencing polymer performance, underscoring the importance of considering solvation environment effects on polymer conformation when designing new mixed conducting CPs for electrochemical applications.
Abstract Conjugated polymers (CPs) with polar side chains can conduct electronic and ionic charges simultaneously, making them promising for bioelectronics, electrocatalysis and energy storage. Recent work showed that adding alkyl spacers between CP backbones and polar side chains improved electronic charge carrier mobility, reduced swelling and enhanced stability, without compromising ion transport. However, how alkyl spacers impact polymer backbone conformation and, subsequently, electronic properties remain unclear. In this work, we design two oxy‐bithiophene‐based CP series, each featuring progressively extended alkyl spacer lengths and two distinct molecular weight (MW) distributions. Using operando characterisations, we evaluate the (spectro)electrochemical and swelling properties of the polymer thin films, and their performance in organic field‐effect transistors and organic electrochemical transistors. Surprisingly, alkyl spacers negatively impact the hole mobility of our polymers, with higher MW amplifying this effect. Using molecular dynamics simulations, we show that it is thermodynamically favourable for adjacent non‐polar alkyl spacers to aggregate in polar electrolytes, leading to backbone twisting. Further spectroscopic measurements corroborate this prediction. Our findings demonstrate the active interactions between side chain structure, MW and electrolyte/solvent polarity in influencing polymer performance, underscoring the importance of considering solvation environment effects on polymer conformation when designing new mixed conducting CPs for electrochemical applications.
Side chain engineering of non-planar zinc( ii ) complexes of azadipyrromethene enables either very high hole mobility, high electron mobility or both as estimated by the space-charge limited current (SCLC) method in diodes.
Organic photovoltaic cells (OPVs) and their compositions are described herein. In one or more embodiments, the OPV or solar cell includes a first electrode (e.g., cathode); a second electrode (e.g., anode); an active layer positioned between the first electrode and the second electrode; and a channel layer positioned between the first electrode and the active layer, wherein the channel layer is configured to laterally disperse a charge across the channel layer. In certain examples, the first electrode is arranged in a grid structure having a plurality of electrode segments and a respective opening between adjacent segments of the first electrode.
The properties of 32K CdZnTe (4 x 4 sq mm large, 2 mm thick) detectors have been studied in the pre-flight calibration of the Burst Alert Telescope (BAT) on-board the Swift Gamma-ray Burst Explorer (scheduled for launch in November 2004). In order to understand the energy response of the BAT CdZnTe array, we first quantify the mobility-lifetime (mu tau) products of carriers in individual CdZnTe detectors, which produce a position dependency in the charge induction efficiency and results in a low energy tail in the energy spectrum. Based on a new method utilizing (57)Co spectra obtained at different bias voltages, the mu tau for electrons ranges from 5.0 x 10(exp -4) to 1.0 x 10(exp -2) sq cm/V while the mu tau for holes ranges from 1.3 x 10(exp -5 to 1.8 x 10(exp -4) sq cm/V. We find that this wide distribution of mu tau products explains the large diversity in spectral shapes between CdZnTe detectors well. We also find that the variation of mu tau products can be attributed to the difference of crystal ingots or manufacturing harness. We utilize the 32K sets of extracted mu tau products to develop a spectral model of the detector. In combination with Monte Carlo simulations, we can construct a spectral model for any photon energy or any incident angle.
This report covers: (1) invention of a new, ultra-low noise, low operating voltage APD which is expected to offer far better performance than the existing volume doped APD device; (2) performance of a comprehensive series of experiments on the acoustic and piezoelectric properties of ZnO films sputtered on GaAs which can possibly lead to a decrease in the required rf drive power for ACT devices by 15dB; (3) development of an advanced, hydrodynamic, macroscopic simulator used for evaluating the performance of ACT and CTD devices and aiding in the development of the next generation of devices; (4) experimental development of CTD devices which utilize a p-doped top barrier demonstrating charge storage capacity and low leakage currents; (5) refinements in materials growth techniques and in situ controls to lower surface defect densities to record levels as well as increase material uniformity and quality.
Singlet-to-triplet intersystem crossing (ISC) in organic molecules is intimately connected with their geometries: by modifying the molecular shape, symmetry selection rules pertaining to spin-orbit coupling can be partially relieved, leading to extra matrix elements for increased ISC. As an analog to this molecular design concept, the study finds that the lattice symmetry of supramolecular polymers also defines their triplet formation efficiencies. A supramolecular polymer self-assembled from weakly interacting molecules is considered. Its 2D oblique unit cell effectively renders it as a coplanar array of 1D molecular columns weakly bound to each other. Using momentum-resolved photoluminescence imaging in combination with Monte Carlo simulations, the study found that photogenerated charge carriers in the supramolecular polymer predominantly recombine as spin-uncorrelated carrier pairs through inter-column charge transfer states. This lattice-defined recombination pathway leads to a substantial triplet formation efficiency (≈60%) in the supramolecular polymer. These findings suggest that lattice symmetry of micro-/macroscopic structures relying on intermolecular interactions can be strategized for controlled triplet formation.
Semiconducting polymers offer synthetic tunability, good mechanical properties, and biocompatibility, enabling the development of soft technologies previously inaccessible. Side-chain engineering is a versatile approach for optimizing these semiconducting materials, but minor modifications can significantly impact material properties and device performance. Carbohydrate side chains have been previously introduced to improve the solubility of semiconducting polymers in greener solvents. Despite this achievement, these materials exhibit suboptimal performance and stability in field-effect transistors. In this work, structure–property relationships are explored to enhance the device performance of carbohydrate-bearing semiconducting polymers. Toward this objective, a series of isoindigo-based polymers with carbohydrate side chains of varied carbon-spacer lengths is developed. Material and device characterizations reveal the effects of side chain composition on solid-state packing and device performance. With this new design, charge mobility is improved by up to three orders of magnitude compared to the previous studies. Processing–property relationships are also established by modulating annealing conditions and evaluating device stability upon air exposure. Notably, incidental oxygen-doping effects lead to increased charge mobility after 10 days of exposure to ambient air, correlated with decreased contact resistance. Bias stress stability is also evaluated. This work highlights the importance of understanding structure–property relationships toward the optimization of device performance
Abstract Many of the studies on the entropy‐stabilized oxide (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O have been heavily application‐based. Previous works have studied effects of cation stoichiometry on the entropy‐driven reaction to form a single phase, but a fundamental exploration of the effects of anion stoichiometry and/or redox chemistry on electrical properties is lacking. Using near‐edge X‐ray absorption fine structure (NEXAFS) and electrical measurements, we show that oxidizing thin film samples of (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O affects primarily the valence of Co, leaving the other cations in this high‐entropy system unchanged. This oxidation increases electrical conduction in these thin films, which occurs via small polaron hopping mediated by the Co valence shift from 2+ to a mixed 2+/3+ state. In parallel, we show that bulk samples sintered in an oxygen‐rich atmosphere have a lower activation energy for electrical conduction than those equilibrated in a nitrogen (reducing) atmosphere. Combining feasible defect compensation scenarios with electrical impedance measurements and NEXAFS data, we propose a self‐consistent interpretation of Co redox‐mediated small polaron conduction as the dominant method of charge transfer in this system.
This project, over its term, included funding to a variety of companies and organizations. In addition to Georgia Tech these included Florida Atlantic University with Dr. William E. Glenn as the P.I., Kodak with Mr. Mike Richardson as the P.I. and M.I.T./Polaroid with Dr. Richard Solomon as the P.I. The focus of the work conducted by these organizations was the development of camera hardware for High Definition Television (HDTV). The focus of the research at Georgia Tech was the development of new semiconductor technology to achieve a next generation solid state imager chip that would operate at a high frame rate (I 70 frames per second), operate at low light levels (via the use of avalanche photodiodes as the detector element) and contain 2 million pixels. The actual cost required to create this new semiconductor technology was probably at least 5 or 6 times the investment made under this program and hence we fell short of achieving this rather grand goal. We did, however, produce a number of spin-off technologies as a result of our efforts. These include, among others, improved avalanche photodiode structures, significant advancement of the state of understanding of ZnO/GaAs structures and significant contributions to the analysis of general GaAs semiconductor devices and the design of Surface Acoustic Wave resonator filters for wireless communication. More of these will be described in the report. The work conducted at the partner sites resulted in the development of 4 prototype HDTV cameras. The HDTV camera developed by Kodak uses the Kodak KAI-2091M high- definition monochrome image sensor. This progressively-scanned charge-coupled device (CCD) can operate at video frame rates and has 9 gm square pixels. The photosensitive area has a 16:9 aspect ratio and is consistent with the "Common Image Format" (CIF). It features an active image area of 1928 horizontal by 1084 vertical pixels and has a 55% fill factor. The camera is designed to operate in continuous mode with an output data rate of 5MHz, which gives a maximum frame rate of 4 frames per second. The MIT/Polaroid group developed two cameras under this program. The cameras have effectively four times the current video spatial resolution and at 60 frames per second are double the normal video frame rate.