Charge selectivity in polymer:Fullerene-based organic solar cells with a chemically linked polyethylenimine interlayer

The power conversion efficiency of solar cells can be optimized via an efficient charge collection by electrodes. In this study, a simple linear polyethylenimine (LPEI), which is an insulating polymer, was adopted as the cathode interfacial layer of poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM)-based bulk-heterojunction organic solar cells (OSCs) with a non-inverted configuration. All photovoltaic parameters of the OSCs were significantly enhanced by depositing LPEI onto the oxygen plasma-treated P3HT:PCBM active layers. The causes of performance enhancement in OSCs were studied. Results revealed that the microstructure and morphology of the P3HT:PCBM layer were almost unaffected by the oxygen plasma treatment and the subsequent LPEI deposition. The X-ray photoelectron spectra of the specimens demonstrated that with the aid of oxygen plasma treatment, the linked LPEI molecules formed a well-aligned dipole layer on top of the P3HT:PCBM layer through the bonding of nitrogen (N) with oxygen (O). The results from quantum chemical calculations showed that the LPEI molecule with an N–O bond had a larger dipole moment at an appropriate direction than that without an N–O bond. By contrast, the LPEI molecules can form a dipole layer with a random orientation in the absence of N–O bonds. The conductive atomic force microscopy images of the specimens showed that the well-aligned dipole layer could facilitate electron transfer and could block hole transfer from the P3HT:PCBM to the cathodes. The well-aligned and augmented interface dipoles improved the charge selectivity at the cathodes and the photovoltaic performance of the devices.     

Preparation and employment of carbon nanodots to improve electron extraction capacity of polyethylenimine interfacial layer for polymer solar cells

The performance of polymer solar cells is substantially enhanced by introducing carbon nanodots as additives in polyethylenimine buffer layer. The most pronounced effect is observed in one type of device with the average power conversion efficiencies increased from 5.78% to 7.56% after the addition of carbon nanodots at an optimal concentration in the interfacial layer, which is mainly attributed to the enhanced light trapping and electron transfer in the devices. Besides the light-harvesting and electron transport capacity improvement, the addition of carbon nanodots can also increase exciton generation and dissociation, leading to a high electron mobility. This study demonstrates a facile approach for enhancing the efficiencies of polymer solar cells.     

Modulations in line shapes of magnetoconductance curves for diodes of pentacene:fullerene charge transfer complexes

This work investigates that the applied electric field modulates the line shapes of magnetoconductance (MC) responses in pentacene:fullerene diodes under illumination. We attribute the line shape of MC curves herein is correlated with the strength of the exchange interaction in pentacene:fullerene charge transfer (CT) complex states. Applying the reversed bias increases the built-in electric field (E_built-in) of the diodes to offset the exchange interaction of CT complex states and narrows the line shapes of MC responses. The saturation field of MC curves in the pentacene:fullerene bulk heterojunction device is 752 Oe when the device is biased at 0.4 V and decreases to 212 Oe at a reversed bias of −1.0 V. The line shape of MC curves for the diode made of pristine pentacene or fullerene as the active layer does not change with the applied bias voltage. Our results indicate the correlations of MC responses with the exchange interaction of CT complexes as modulated by the applied electric field.     

Direct comparison of charge transport and electronic traps in polymer–fullerene blends under dark and illuminated conditions

A direct comparison of charge transport and electronic traps in representative polymer–fullerene blend, poly (3-hexylthiophene) (P3HT) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 (PCBM), is carried out in dark and illuminated conditions based on the measurements of temperature-dependent current–voltage characteristics. In dark condition, the charge transport presents a transition from Ohmic to trap-limited current. While the trap-filled space charge limited current is observed under illumination at the same applied bias. From evaluations of trap density and energy distribution by a differential method, it is reveal that the diverse charge transport in dark and illuminated conditions is mainly caused by the different trap states distribution, which strongly affects the space charges and the electrical field in P3HT: PCBM blends.     

Nondimensional frequency scaling of aerodynamically-tensioned membranes

Membrane wings have applications that involve low Reynolds number flyers such as micro air vehicles. The time-averaged and time-dependent deformations of the membrane affect the aerodynamic characteristics of the wing, primarily in the region beyond the maximum aerodynamic efficiency of the wing. This paper investigates an appropriate nondimensional vibration frequency scaling of a spanwise tensioned membrane with free (unattached) leading and trailing edges at low Reynolds numbers relative to nondimensional aeroelastic parameters. Silicone rubber membranes with varying spanwise pre-tension, aerodynamic tension (due to wing angle-of-attack and flow dynamic pressure), modulus of elasticity, span, and thickness are studied. Experimental results are compared to a proposed scaling that simplifies the aerodynamic loading as a uniform pressure distribution acting on the membrane. Data is further compared and discussed relative to previous published results of membrane wings with finite wing spans (three-dimensional flow) and fixed (rigid) leading edges.     

Single determinant N‐representability and the kernel energy method applied to water clusters

The Kernel energy method (KEM) is a quantum chemical calculation method that has been shown to provide accurate energies for large molecules. KEM performs calculations on subsets of a molecule (called kernels) and so the computational difficulty of KEM calculations scales more softly than full molecule methods. Although KEM provides accurate energies those energies are not required to satisfy the variational theorem. In this article, KEM is extended to provide a full molecule single‐determinant N‐representable one‐body density matrix. A kernel expansion for the one‐body density matrix analogous to the kernel expansion for energy is defined. This matrix is converted to a normalized projector by an algorithm due to Clinton. The resulting single‐determinant N‐representable density matrix maps to a quantum mechanically valid wavefunction which satisfies the variational theorem. The process is demonstrated on clusters of three to twenty water molecules. The resulting energies are more accurate than the straightforward KEM energy results and all violations of the variational theorem are resolved. The N‐representability studied in this article is applicable to the study of quantum crystallography. © 2017 Wiley Periodicals, Inc.     

Electronic structure of stable n-type semiconducting molecular complex (diC8-BTBT)(TCNQ) studied by ultraviolet photoemission and inverse photoemission spectroscopy

The electronic structure of a semiconducting mixed-stack charge transfer (CT) complex composed of a 2,7-dialkyl[1]benzothieno[3,2-b][1] benzothiophene (diC₈-BTBT) electron donor and a tetracyanoquinodimethane (TCNQ) electron acceptor, (diC₈-BTBT)(TCNQ), was studied by ultraviolet photoemission spectroscopy and inverse photoemission spectroscopy. Compared with its components, the frontier electronic states observed for the (diC₈-BTBT)(TCNQ) complex showed a large stabilization that originates from the reconstruction of electronic states by intermolecular donor-acceptor CT interactions. We discuss how the frontier electronic states of the complex are formed from those of the individual component molecules, and clarify the origin of the air-stable n-type organic field-effect transistor characteristics that the material exhibits when it is used as a channel semiconductor.     

Enhanced luminescence of CaSb2O6:Bi3+ blue phosphors by efficient charge compensation

This paper reported an enhanced photoluminescence of CaSb₂O₆:Bi³⁺ by efficient charge compensation. Charge compensated CaSb₂O₆:Bi³⁺,M⁺ (M=Li, Na and K) phosphors were prepared using a co-precipitation technique followed by heat-treatment. The structure and morphology of the as-prepared CaSb₂O₆:Bi³⁺,M⁺ samples were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results revealed that the obtained CaSb₂O₆:Bi³⁺,M⁺ samples are hexagonal crystal structure and this structure was retained regardless of co-doping by Li⁺, Na⁺ or K⁺. All samples showed sphere-like shape with particle size of 40–80 nm. The optical properties of products were studied by UV–vis diffuse reflectivity, photoluminescence spectra and luminescence decay measurements. Under the excitation of 336 nm light, all of the samples exhibited a strong blue emission peaking around 437 nm, which is attributed to the ³P₁–¹S₀ transition of the Bi³⁺ ion. It was found that the charge compensation has significant effect on the photoluminescence properties of CaSb₂O₆:Bi³⁺ and the best luminescence properties have been achieved for CaSb₂O₆:0.75Bi³⁺,0.75 Na⁺. The mechanism for the enhancement of the blue emission has also been studied in detail. Our results suggested that the optical properties of oxide nanostructures can be tailored through co-doping with aliovalent ions and the favorable luminescence properties of CaSb₂O₆:Bi³⁺,Na⁺ make it potential for lighting and display applications.     

The role of the electrode configuration on the electrical properties of small-molecule semiconductor thin-films

This paper presents a systematic analysis of the electrode configuration influence on the electrical properties of organic semiconductor (OSC) thin-film devices. We have fabricated and electrically characterized a set of planar two-terminal devices. The differences in I-V characteristics between the top and bottom contact structures are presented and analyzed. Top-contact configurations have a linear current vs. electric field behavior, while the bottom-electrode devices display a transition from ohmic to space-charge-limited conduction regime. The transition is temperature- and thickness-dependent. Finite-element calculations show that when the OSC film is connected using top electrodes, the current flows through the OSC bulk region. On the other hand, the bottom-electrode configuration allows most of the current to flow near the OSC/substrate interface. The current probes interfacial states resulting in a space-charge conduction regime. The results shed some light on the so-called “contact effects” commonly observed in organic thin-film transistors. The findings presented here have implications for both the understanding of the charge transport in OSC films and the design of organic semiconductor devices.