Solution-Processed Phototransistors Combining Organic Absorber and Charge Transporting Oxide for Visible to Infrared Light Detection.

This report demonstrates high-performance infrared phototransistors that use a broad-band absorbing organic bulk heterojunction (BHJ) layer responsive from the visible to the shortwave infrared, from 500 to 1400 nm. The device structure is based on a bilayer transistor channel that decouples charge photogeneration and transport, enabling independent optimization of each process. The organic BHJ layer is improved by incorporating camphor, a highly polarizable additive that increases carrier lifetime. An indium zinc oxide transport layer with high electron mobility is employed for rapid charge transport. As a result, the phototransistors achieve a dynamic range of 127 dB and reach a specific detectivity of 5 × 1012 Jones under a low power illumination of 20 nW/cm2, outperforming commercial germanium photodiodes in the spectral range below 1300 nm. The photodetector metrics are measured with respect to the applied voltage, incident light power, and temporal bandwidth, demonstrating operation at a video-frame rate of 50 Hz. In particular, the frequency and light dependence of the phototransistor characteristics are analyzed to understand the change in photoconductive gain under different working conditions

Synthesis and Characterization of [Fe(Htrz)\u3csub\u3e2\u3c/sub\u3e(trz)](BF\u3csub\u3e4\u3c/sub\u3e)] Nanocubes

Compounds that exhibit spin-crossover (SCO) type behavior have been extensively investigated due to their ability to act as molecular switches. Depending on the coordinating ligand, in this case 1H-1,2,4-triazole, and the crystallite size of the SCO compound produced, the energy requirement for the spin state transition can vary. Here, SCO [Fe(Htrz)2(trz)](BF4)] nanoparticles were synthesized using modified reverse micelle methods. Reaction conditions and reagent ratios are strictly controlled to produce nanocubes of 40–50 nm in size. Decreases in energy requirements are seen in both thermal and magnetic transitions for the smaller sized crystallites, where, compared to bulk materials, a decrease of as much as 20 °C can be seen in low to high spin state transitions

Broadband Infrared Photodetection Using a Narrow Bandgap Conjugated Polymer

Photodetection spanning the short-, mid-, and long-wave infrared (SWIR-LWIR) underpins modern science and technology. Devices using state-of-the-art narrow bandgap semiconductors require complex manufacturing, high costs, and cooling requirements that remain prohibitive for many applications. We report high-performance infrared photodetection from a donor-acceptor conjugated polymer with broadband SWIR-LWIR operation. Electronic correlations within the π-conjugated backbone promote a high-spin ground state, narrow bandgap, long-wavelength absorption, and intrinsic electrical conductivity. These previously unobserved attributes enabled the fabrication of a thin-film photoconductive detector from solution, which demonstrates specific detectivities greater than 2.10 × 109 Jones. These room temperature detectivities closely approach those of cooled epitaxial devices. This work provides a fundamentally new platform for broadly applicable, low-cost, ambient temperature infrared optoelectronics

Organic Bulk Heterojunction Infrared Photodiodes for Imaging Out to 1300 nm

This work studies organic bulk heterojunction photodiodes with a wide spectral range capable of imaging out to 1.3 μm in the shortwave infrared. Adjustment of the donor-to-acceptor (polymer:fullerene) ratio shows how blend composition affects the density of states (DOS) which connects materials composition and optoelectronic properties and provides insight into features relevant to understanding dispersive transport and recombination in the narrow bandgap devices. Capacitance spectroscopy and transient photocurrent measurements indicate the main recombination mechanisms arise from deep traps and poor extraction from accumulated space charges. The amount of space charge is reduced with a decreasing acceptor concentration; however, this reduction is offset by an increasing trap DOS. A device with 1:3 donor-to-acceptor ratio shows the lowest density of deep traps and the highest external quantum efficiency among the different blend compositions. The organic photodiodes are used to demonstrate a single-pixel imaging system that leverages compressive sensing algorithms to enable image reconstruction

Ultrafast High-Energy Micro-Supercapacitors Based On Open-Shell Polymer-Graphene Composites

Micro-supercapacitors are poised to serve as on-chip power sources for electronics. However, the challenge to simultaneously increase their power, energy, and lifetime demands new material combinations beyond current carbon-based systems. Here, we demonstrate that electro-deposition of an open-shell conjugated polymer with reduced graphene oxide achieves electrodes with capacitance up to 186 mF cm−2 (372 F cm−3). The extended delocalization within the open-shell polymer stabilizes redox states and facilitates a 3 V wide potential window, while the hierarchical electrode structure promotes ultrafast kinetics. The micro-supercapacitor shows a high power density of 227 mW cm−2 with an energy density of 10.5 μWh cm−2 and stability of 84% capacitance retention after 11,000 cycles. These attributes allow operation at 120 Hz for fast charging and alternating current (AC) line filtering applications, which may be suitable to replace bulky electrolytic capacitors or serve as high-endurance energy storage for wireless electronics

A High-Spin Ground-State Donor-Acceptor Conjugated Polymer

Interest in high-spin organic materials is driven by opportunities to enable far-reaching fundamental science and develop technologies that integrate light element spin, magnetic, and quantum functionalities. Although extensively studied, the intrinsic instability of these materials complicates synthesis and precludes an understanding of how fundamental properties associated with the nature of the chemical bond and electron pairing in organic materials systems manifest in practical applications. Here, we demonstrate a conjugated polymer semiconductor, based on alternating cyclopentadithiophene and thiadiazoloquinoxaline units, that is a ground-state triplet in its neutral form. Electron paramagnetic resonance and magnetic susceptibility measurements are consistent with a high-to-low spin energy gap of 9.30 × 10−3 kcal mol−1. The strongly correlated electronic structure, very narrow bandgap, intramolecular ferromagnetic coupling, high electrical conductivity, solution processability, and robust stability open access to a broad variety of technologically relevant applications once thought of as beyond the current scope of organic semiconductors

Topology and Ground State Control In Open-Shell Donor-Acceptor Conjugated Polymers

Donor-acceptor (DA) conjugated polymers (CPs) with narrow bandgaps and open-shell (diradical) character represent an emerging class of materials whose rich behavior emanates from their collective electronic properties and diminished electron pairing. However, the structural and electronic heterogeneities that define these materials complicate bandgap control at low energies and connections linking topology, exchange interactions, and (opto)electronic functionality remain nascent. To address these challenges, we demonstrate structurally rigid and strongly π-conjugated copolymers comprised of a solubilizing thiadiazoloquinoxaline acceptor and cyclopenta[2,1-b:3,4-b′]dithiophene or dithieno[3,2-b:2′,3′-d]thiophene donors. Atom-specific substitution modulates local aromatic character within the donor resulting in dramatic differences in structural, physicochemical, electronic, and magnetic properties of the polymers. These long-range π-mediated interactions facilitate control between low-spin aromatic and high-spin quinoidal forms. This work provides a strategy to understand the evolution of the electronic structure within DA CPs, control the ground state spin multiplicity, tune spin-spin interactions, and articulate the emergence of their novel properties

Financing of U.S. Biomedical Research and New Drug Approvals across Therapeutic Areas

We estimated U.S. biomedical research funding across therapeutic areas, determined the association with disease burden, and evaluated new drug approvals that resulted from this investment.We calculated funding from 1995 to 2005 and totaled Food and Drug Administration approvals in eight therapeutic areas (cardiovascular, endocrine, gastrointestinal, genitourinary, HIV/AIDS, infectious disease excluding HIV, oncology, and respiratory) primarily using public data. We then calculated correlations between funding, published estimates of disease burden, and drug approvals. Financial support for biomedical research from 1995 to 2005 increased across all therapeutic areas between 43% and 369%. Industry was the principal funder of all areas except HIV/AIDS, infectious disease, and oncology, which were chiefly sponsored by the National Institutes of Health (NIH). Total (rho = 0.70; P = .03) and industry funding (rho = 0.69; P = .04) were correlated with projected disease burden in high income countries while NIH support (rho = 0.80; P = .01) was correlated with projected disease burden globally. From 1995 to 2005 the number of new approvals was flat or declined across therapeutic areas, and over an 8-year lag period, neither total nor industry funding was correlated with future approvals.Across therapeutic areas, biomedical research funding increased substantially, appears aligned with disease burden in high income countries, but is not linked to new drug approvals. The translational gap between funding and new therapies is affecting all of medicine, and remedies must include changes beyond additional financial investment

Modular Conjugated Polymers for Mid-Infrared Photonic Applications

Over the course of the project related to the development of conjugated polymers for optical to electrical signal transduction of infrared IR light we have made significant strides in many of the originally-proposed research areas. Namely, we have 1 continued to demonstrate the capability to systematically and precisely control the properties of donor-acceptor DA conjugated polymers CPs extending throughout the short-, mid-wavelength infrared MWIR1.4-8 unit vector 14m and long-wavelength infrared LWIR 814 unit vector 14m 2 demonstrated improvements in the capability to control the electronic structure of narrow bandgap conjugated polymers leading to the discovery of new phenomena and functionality from organic materials 3 developed new materials and devices enabling the first examples of photodetection from the SWIR-LWIR using organic materials and 4 demonstrated high performance photoconductive devices that outperform their inorganic counterparts through collaborative efforts with AFRL. Thus, we have been able to advance the design of organic semiconductors OSCs enabling new classes of materials, new optoelectronic and physical functionality, and new device technologies. Moreover, funding of this work by the AFOSR has allowed our team to become a world leader in the chemistry, photophysics, and solid-state device applications of narrow bandgap and open-shell CPs and organic infrared optoelectronics. We have continued to make additional significant discoveries in narrow bandgap materials such as ground state electronics that can be manipulated, conductivities that are higher than other neutral organic solids and demonstrate unique electrical, optical, spin, thermal, magnetic, and quantum phenomena