Efficient organic photovoltaic cells based on thiazolothiazole and benzodithiophene copolymers with π‐conjugated bridges

New donor–π–acceptor (D–π–A) type conjugated copolymers, poly[(4,8‐bis((2‐hexyldecyl)oxy)benzo[1,2‐b:4,5‐b′]dithiophene)‐alt‐(2,5‐bis(4‐octylthiophen‐2‐yl)thiazolo[5,4‐d]thiazole)] (PBDT‐tTz), and poly[(4,8‐bis((2‐hexyldecyl)oxy)benzo[1,2‐b:4,5‐b′]dithiophene)‐alt‐(2,5‐bis(6‐octylthieno[3,2‐b]thiophen‐2‐yl)thiazolo[5,4‐d]thiazole)] (PBDT‐ttTz) were synthesized and characterized with the aim of investigating their potential applicability to organic photovoltaic active materials. While copolymer PBDT‐tTz showed a zigzagged non‐linear structure by thiophene π‐bridges, PBDT‐ttTz had a linear molecular structure with thieno[3,2‐b]thiophene π‐bridges. The optical, electrochemical, morphological, and photovoltaic properties of PBDT‐tTz and PBDT‐ttTz were systematically investigated. Furthermore, bulk heterojunction photovoltaic devices were fabricated by using the synthesized polymers as p‐type donors and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester as an n‐type acceptor. PBDT‐ttTz showed a high power conversion efficiency (PCE) of 5.21% as a result of the extended conjugation arising from the thienothiophene π‐bridges and enhanced molecular ordering in the film state, while PBDT‐tTz showed a relatively lower PCE of 2.92% under AM 1.5 G illumination (100 mW/cm²). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1978–1988     

Some exact solutions of generalized Zakharov system

In this paper, we seek exact solutions of generalized Zakharov system. We use extended trial equation method to obtain exact solutions of this system. Consequently, we obtain some exact solutions including soliton solutions, rational, Jacobi elliptic and hyperbolic function solutions of this system by using extended trial equation method.     

Photosensitivity,substituent and solvent-induced shifts in UV-visible absorption bands of naphthyl-ester liquid crystals: a comparative theoretical approach

The substituent- and solvent-induced shifts in UV-visible absorption bands of naphthyl-ester nematic liquid crystals, viz., 4-octylphenyl-6-octyloxy-2-naphthoate (NAPHE1) and 6-octyloxy-2-naphthylyl-4-octyloxybenzoate (NAPHE2), have been investigated using the DFT, CNDO/S and INDO/S methods. A correlation has been made between molecular charge distribution and phase stability based on Mulliken, Loewdin, AM1, PM3, MNDO, CNDO/S and INDO/S methods. The observed π→π* and n→π* electronic transitions have been reported. The substituent- and solvent-induced shifts in absorption bands, transition energies and energy gaps have been discussed. The photosensitivity of the molecules has been analysed based on these shifts. It has been observed that the substituent has a dominant role on both absorption maxima and energy band gap, whereas the solvent has a dominant role only on absorption maxima, and no effect has been observed on the energy gap. These shifts may provide beneficial consequences in determining the end use of compounds.     

Isoregic Thienylene‐Phenylene Polymers: The Effects of Structural Variation and Application to Photovoltaic Devices

Isoregic conjugated polymers composed of thiophene and dialkoxybenzene units were designed to harvest incident light in the mid‐visible energy range (band gap of 2.1 eV). Poly(1,4‐bis(2‐thienyl)‐2,5‐diheptoxybenzene) (PBTB(OC₇H₁₅)₂) and poly(1,4‐bis(2‐thienyl)‐2,5‐didodecyloxybenzene) (PBTB(OC₁₂H₂₅)₂) have shown significant photovoltaic performance as an electron donor when used in tandem with the electron acceptor [6, 6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) in bulk hetero‐junction photovoltaic devices. Photovoltaic devices incorporating PBTB(OC₇H₁₅)₂ and PCBM have shown AM1.5 efficiencies of ～0.6% with a short circuit current density of 2.5 mA/cm², an open circuit voltage of 0.74 V, and a fill factor of 0.32. Incident Photon‐to‐Current Efficiency (IPCE) of the device was found to be ca. 16% at 410 nm. In order to examine the relationship between the molecular structure of the polymers and their electronic energy levels, and to correlate this with photovoltaic performance, optoelectronic and electrochemical results are discussed in relation to the I‐V characteristics of the devices. Additionally, a computer‐aided simulation is used to gain further insight into the effect of polymer structure on the energetic relationships in the bulk heterojunction devices.     

Y,Zr,Nb掺杂SnO_2电子结构的第一性原理研究

本文基于第一性原理方法研究了Y,Zr,Nb在Sn位掺杂SnO_2的键长变化、稳定性、能带结构以及态密度.结果表明:Y,Zr,Nb在Sn位掺杂SnO_2使附近的键长发生改变,改变量最大是Y掺杂SnO_2体系;掺杂体系的杂质替换能都为负值,表明体系为稳定结构;掺杂使SnO_2能级增多,能较好的调节带隙值;而Y掺杂SnO_2体系价带顶端有一条能级越过了费米线表明该体系呈现出半导体的特征;同时,Y,Zr,Nb掺杂SnO_2使导带底端的能级出现分离;在低能区的态密度仍主要由Sn、O的s轨道贡献;在高能区态密度的掺杂体系出现sp杂化的现象; Zr掺杂SnO_2的态密度能量向低能区移动.     

Synthesis and photovoltaic properties of conjugated side chains polymers with different electron‐withdrawing and donating end groups

A series of novel low band gap polymers containing conjugated side chains with 4,7‐dithien‐5‐yl‐2,1,3‐benzodiathiazole and different electron‐withdrawing end groups of aldehyde ( PT‐DTBTCHO ), 2‐ethylhexyl cyanoacetate ( PT‐DTBTCN ), 1,3‐diethyl‐2‐thiobarbituric acid ( PT‐DTBTDT ), and electron‐donating end group of 2‐methylthiophene ( PT‐DTBTMT ) have been designed and synthesized. All polymers exhibit good solubility in common organic solvents, film‐forming ability, and thermal stability. These conjugated polymers show the broad ultraviolet‐visible absorption and the narrow optical band gaps in the range of 1.65–1.90 eV. Through changing the end group of conjugated side chains, the photophysical properties and energy levels of the polymers were tuned effectively. Bulk heterojunction solar cells based on the blend of these polymers and (6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) reached the best power conversion efficiency (PCE) of 2.72%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Assessing the Calibration of High-Dimensional Ensemble Forecasts Using Rank Histograms

Any decision-making process that relies on a probabilistic forecast of future events necessarily requires a calibrated forecast. This article proposes new methods for empirically assessing forecast calibration in a multivariate setting where the probabilistic forecast is given by an ensemble of equally probable forecast scenarios. Multivariate properties are mapped to a single dimension through a prerank function and the calibration is subsequently assessed visually through a histogram of the ranks of the observation’s preranks. Average ranking assigns a prerank based on the average univariate rank while band depth ranking employs the concept of functional band depth where the centrality of the observation within the forecast ensemble is assessed. Several simulation examples and a case study of temperature forecast trajectories at Berlin Tegel Airport in Germany demonstrate that both multivariate ranking methods can successfully detect various sources of miscalibration and scale efficiently to high-dimensional settings. Supplemental material in form of computer code is available online.     

Carbon dioxide adsorption studies on delafossite CuFeO2 hydrothermally synthesized

Delafossite CuFeO₂ oxide was synthesized by a hydrothermal technique using Cu₂O and FeOOH as precursors with the addition of fused NaOH as mineralizer. The amount of rhombohedral and hexagonal delafossite phase formed depends on the synthesis time lapses between 2 and 5 days and on the NaOH concentration. The compounds obtained were analyzed with Raman Spectroscopy, X-Ray Diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) in order to obtain their morphological and structural properties. Optical behavior was studied by UV–vis Spectroscopy and gas adsorption measured with a Quartz-Crystal Microbalance (QCM). Our results show that this type of hydrothermal synthesis is capable of recreating the delafossite-type structure of copper-iron oxide and produces a high yield of material with the right stoichiometry. The highest uptake of carbon dioxide is observed on the sample with the highest ratio between rhombohedral and hexagonal delafossite phase.     

What can statistical process control show us about ionization chamber stability?

PurposeStatistical process control (SPC) has been shown to be a suitable tool for medical physicists to monitor quality and keep variability low and within specifications. We report our findings regarding ionisation chamber stability in our department when using a radioactive stability check device (RSCD) and we compare them with similar previously published records, including calibration results.MethodsWe retrospectively studied the stability of a PPC 40 parallel-plate chamber, and two Farmer chambers (FC65-G and FC65-P) by checking them with dedicated RSCDs. We analysed the data following SPC methodology which includes plotting I-MR control charts, monitoring out-of-control observations, calculating process capability ratios (C_p), and estimating conformance to specifications. We also estimated the C_p and adherence to specifications of previously published data.ResultsThe PPC40 chamber hardly went out of the control limits over the whole six-year period assessed. However, Farmer chamber verifications drifted in opposite directions in phase II, and the deviations observed did not agree with their calibration records, which only increased by a maximum of 0.5%. In phase I the most unstable chamber was the FC65-P with a C_p equal to 0.9 at a specification level of ±1%. The PPC40 chamber was stable to within a maximum C_p of 1.3. Several sets of analysed data, including ours and those from other authors, fitted well within these limits: within ±1.9% and ±1.5% for a C_p of 1.5 and 1.33 respectively.ConclusionsSPC with constant long-term RSCD checking gave us a meaningful plot of the instability of our ionisation chambers. Although a period of two years between calibrations should not be surpassed, in the interim this check can conform to specifications of ±1.5%.     

Color tuning of up-conversion emission in ytterbium,erbium, aluminum tri-doped zinc oxide crystal by adjusting aluminum concentration

Ytterbium, erbium, aluminum tri-doped zinc oxide crystal was synthesized, which can turn color from red to green up-conversion luminescence through adjusting aluminum content. When the aluminum concentration reached 4?mol%, the color of up-conversion emission first turn from red to green. Meanwhile, the ratio of red to green emission reduced from 25.32 to 0.26, and the coordinates of chromaticity coordinate calculation changes from (0.5749, 0.3378) to (0.2190, 0.7169) with aluminum concentration range from 0 to 4?mol%. The up-conversion emission peaks at 521, 542, and 660?nm of sample originate from the transitions of ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2, and ⁴F_9/2 → ⁴I_15/2 of erbium ions, respectively. X-ray diffraction patterns perform the better crystallization degree with increasing aluminum concentration. The scanning electron microscopy images show the porous and lamellar structures with different aluminum concentrations. A convenient but effective design to obtain ytterbium, erbium, aluminum tri-doped zinc oxide up-conversion luminescence is reported, which can turn color from red to green.