Study of the Hole Transport Processes in Solution-Processed Layers of the Wide Bandgap Semiconductor Copper(I) Thiocyanate (CuSCN)

Wide bandgap hole-transporting semiconductor copper(I) thiocyanate (CuSCN) has recently shown promise both as a transparent p-type channel material for thin-film transistors and as a hole-transporting layer in organic light-emitting diodes and organic photovoltaics. Herein, the hole-transport properties of solution-processed CuSCN layers are investigated. Metal-insulator-semiconductor capacitors are employed to determine key material parameters including: dielectric constant [5.1 (±1.0)], flat-band voltage [-0.7 (±0.1) V], and unintentional hole doping concentration [7.2 (±1.4) × 1017 cm-3]. The density of localized hole states in the mobility gap is analyzed using electrical field-effect measurements; the distribution can be approximated invoking an exponential function with a characteristic energy of 42.4 (±0.1) meV. Further investigation using temperature-dependent mobility measurements in the range 78-318 K reveals the existence of three transport regimes. The first two regimes observed at high (303-228 K) and intermediate (228-123 K) temperatures are described with multiple trapping and release and variable range hopping processes, respectively. The third regime observed at low temperatures (123-78 K) exhibits weak temperature dependence and is attributed to a field-assisted hopping process. The transitions between the mechanisms are discussed based on the temperature dependence of the transport energy. The wide bandgap p-type semiconductor copper(I) thiocyanate (CuSCN) has the potential to replace conventional hole-transport materials in numerous opto/electronics applications. This work provides a comprehensive analysis of the charge transport properties of solution-processed CuSCN layers. Various techniques are employed to evaluate the dielectric constant, flat-band voltage, unintentional doping concentration, density of states in the mobility gap, and hole-transport mechanisms.Department of Applied PhysicsMaterials Research Centr

p-channel thin-film transistors based on spray-coated Cu2O films

Thin films of cuprous oxide (Cu2O) were grown using solution-based spray pyrolysis in ambient air and incorporated into hole-transporting thin-film transistors. The phase of the oxide was confirmed by X-ray diffraction measurements while the optical band gap of the films was determined to be ∼2.57 eV from optical transmission measurements. Electrical characterization of Cu2O films was performed using bottom-gate, bottom-contact transistors based on SiO2 gate dielectric and gold source-drain electrodes. As-prepared devices show clear p-channel operation with field-effect hole mobilities in the range of 10−4–10−3 cm2 V−1 s−1 with some devices exhibiting values close to 1 × 10−2 cm2 V−1 s−1

Ternary organic photodetectors based on pseudo–binaries nonfullerene–based acceptors

The addition of a third component to a donor:acceptor blend is a powerful tool to enhance the power conversion efficiency of organic solar cells. Featuring a similar operating mechanism, organic photodetectors are also expected to benefit from this approach. Here, we fabricated ternary organic photodetectors, based on a polymer donor and two nonfullerene acceptors, resulting in a low dark current of 0.42 nA cm−2 at −2 V and a broadband specific detectivity of 1012 Jones. We found that exciton recombination in the binary blend is reduced in ternary devices due to the formation of a pseudo-binary microstructure with mixed donor–acceptor phases. With this approach a wide range of intermediate open-circuit voltages is accessible, without sacrificing light-to-current conversion. This results in ternary organic photodetector (TOPD) with improved Responsivity values in the near-infrared. Moreover, morphology analyses reveal that TOPD devices showed improved microstructure ordering and consequentially higher charge carrier mobilities compared to the reference devices

The influence of backbone fluorination on the dielectric constant of conjugated polythiophenes

The ability to modify or enhance the dielectric constant of semiconducting polymers can prove valuable for a range of optoelectronic and microelectronic applications. In the case of organic photovoltaics, increasing the dielectric constant of the active layer has often been suggested as a method to control charge generation, recombination dynamics, and ultimately, the power conversion efficiencies. In this contribution, the impact that the degree and pattern of fluorination has on the dielectric constant of poly(3-octylthiophene) (P3OT), a more soluble analogue of the widely studied conjugated material poly(3-hexylthiophene), is explored. P3OT and its backbone-fluorinated analogue, F-P3OT, are compared along with a block and alternating copolymer version of these materials. It is found that the dielectric constant of the polymer thin films increases as the degree of backbone fluorination increases, in a trend consistent with density functional theory calculations of the dipole moment

Effect of Systematically Tuning Conjugated Donor Polymer Lowest Unoccupied Molecular Orbital Levels via Cyano Substitution on Organic Photovoltaic Device Performance

We report a systematic study into the effects of cyano substitution on the electron accepting ability of the common acceptor 4,7-bis(thiophen-2-yl)-2,1,3-benzothiadiazole (DTBT). We describe the synthesis of DTBT monomers with either 0, 1, or 2 cyano groups on the BT unit and their corresponding copolymers with the electron rich donor dithienogermole (DTG). The presence of the cyano group is found to have a strong influence on the optoelectronic properties of the resulting donor–acceptor polymers, with the optical band gap red-shifting by approximately 0.15 eV per cyano substituent. We find that the polymer electron affinity is significantly increased by ∼0.25 eV upon addition of each cyano group, while the ionization potential is less strongly affected, increasing by less than 0.1 eV per cyano substituent. In organic photovoltaic (OPV) devices power conversion efficiencies (PCE) are almost doubled from around 3.5% for the unsubstituted BT polymer to over 6.5% for the monocyano substituted BT polymer. However, the PCE drops to less than 1% for the dicyano substituted BT polymer. These differences are mainly related to differences in the photocurrent, which varies by 1 order of magnitude between the best (1CN) and worst devices (2CN). The origin of this variation in the photocurrent was investigated by studying the charge generation properties of the photoactive polymer–fullerene blends using fluorescence and transient absorption spectroscopic techniques. These measurements revealed that the improved photocurrent of 1CN in comparison to 0CN was due to improved light harvesting properties while maintaining a high exciton dissociation yield. The addition of one cyano group to the BT unit optimized the position of the polymer LUMO level closer to that of the electron acceptor PC71BM, such that the polymer’s light harvesting properties were improved without sacrificing either the exciton dissociation yield or device VOC. We also identify that the drop in performance for the 2CN polymer is caused by very limited yields of electron transfer from the polymer to the fullerene, likely caused by poor orbital energy level alignment with the fullerene acceptor (PC71BM). This work highlights the impact that small changes in chemical structure can have on the optoelectronic and device properties of semiconducting polymer. In particular this work highlights the effect of LUMO–LUMO offset on the excited state dynamics of polymer–fullerene blends

Tuning of emission color for blue dendrimer blend light-emitting diodes

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Stress echocardiography in elderly patients with coronary artery disease Applicability, safety and prognostic value of dobutamine and adenosine echocardiography in elderly patients

AbstractObjectives. Our aim was to determine the applicability, safety and prognostic value of adenosine and dobutamine stress echocardiography in patients ≥70 years old.Background. These tests are sometimes mandatory because of difficulties and inaccuracies in interpreting traditional electrocardiographic stress tests. Furthermore, if these tests could be used to avoid coronary arteriography and cardiac catheterization, they would become essential in the care of the elderly, whose numbers are increasing.Methods. We performed coronary arteriography and dobutamine and adenosine stress echocardiographic tests in 120 patients (72 men) ≥70 years old who entered the hospital because of chest pain and had known or suspected coronary artery disease. The stress tests were performed on separate days, within 2 weeks of coronary arteriography. Both the arteriograms and the echocardiograms were analyzed by two experts who had no knowledge of the patients' other data or the other interpreter's report. Tests were judged to have positive or negative results, and the patients were followed up for the development of cardiac events. Univariate and multivariate analyses and other statistical modalities were applied for comparisons.Results. Documented coronary artery disease was found in 89 patients. During the 14 ± 7 months of follow-up, cardiac events developed in 50 patients, including 3 (7.9%) of 38 patients with negative dobutamine and 12 (20.7%) of 58 patients with negative adenosine test results. Demonstration of any abnormality on stress echocardiography was an independent factor for cardiac events, both for dobutamine (relative risk 7.3) and for adenosine (relative risk 3.0). Both cessation of dobutamine or adenosine tests and diagnosis of disease in two or more coronary vessels were also independent predictors. ST segment depression ≥1 mm was related to future events only with the dobutamine test.Conclusions. These echocardiographic stress tests proved safe and well tolerated. They successfully stratified this cohort of elderly patients with coronary artery disease to low or high risk subgroups for subsequent cardiac events

Nondispersive hole transport in a spin-coated dendrimer film measured by the charge-generation-layer time-of-flight method

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