Effects of solvent vapor annealing on the optical properties and surface adhesion of conjugated D : A thin films.

A diketopyrrolopyrrole (DPP) and perylene diimide (PDI)-based molecule, denoted as PDI-DPP-PDI, was investigated as an electron acceptor material in bulk heterojunction (BHJ) solar cells, with poly[[4,8-bis [5-(2-ethylhexyl)-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl] [2-(2-ethyl-1-oxohexyl)thieno[3,4-b]thiophenediyl]] (PBDTTT-CT) as an electron donor. The donor polymer and the acceptor molecule have complementary absorption spectra, which is an essential feature for energy collection in organic solar cells. However, AFM images indicated the presence of isolated and microsized PDI-DPP-PDI domains along the surface of the films, which reduced the power conversion efficiency. Therefore, to improve the homogenization of the acceptor along the film, a post-deposition treatment, denoted as solvent vapor annealing (SVA), was performed in a saturated atmosphere containing the vapour of an organic solvent for 3-10 minutes. This procedure changed the optical and morphological properties of the PBDTTT-CT : PDI-DPP-PDI active layer, resulting in increased power conversion efficiency values by more than 2.5 times (reaching 5.1%). Theoretical simulation pointed out that the experimental absorbance band localized at 580 nm, which appeared after SVA treatment, is possibly related to an intense simulated band with a maximum at 572 nm, resulting from a pair of transitions starting in the copolymer and ending in PDI-DPP-PDI, in regions where both are stacked at about 3 Å. The most significant natural transition orbitals (NTOs) related to these transitions indicated charge transfer character. Moreover, analyses carried out by power spectrum density (PDS) of images acquired from the SVA-treated film indicated that in the region of larger frequencies, across the length scale at around 30-70 nm, an additional fractal region appeared with a Ds of 0.95, indicating a flattened region, possibly related to changes in the overall conformation after SVA treatment. This indicates an improvement in the molecular packing, a feature not observed in the as-cast film. The analyses by force curve spectroscopy pointed out increased adhesion forces and adhesion energy in the PBDTTT-CT : PDI-DPP-PDI film after SVA treatment; this feature enhanced the interfacial interaction with the top electrodes, reflecting improved charge extraction in the photovoltaic device.

Defect chemistry and relaxation processes: effect of an amphoteric substituent in lead-free BCZT ceramics.

The effect of praseodymium (Pr), an amphoteric substituent, on phase transition, dielectric relaxation and electrical conductivity has been studied and analysed in 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 (BCZT) ceramics synthesized by a solid state reaction method. Structural investigations showed co-existence of two phases - tetragonal (P4mm) and rhombohedral (R3m) - for compositions with x ≤ 0.05 wt% Pr. Temperature dependent dielectric studies revealed two phase transitions - rhombohedral (R) → tetragonal (T) and T → cubic (C) - that gradually evolved into one T → C transition for x > 0.05 wt% Pr in BCZT. A dielectric relaxation behaviour was observed in the temperature range of 275-500 °C that was attributed to the localized relaxation process (short-range hopping motion of oxygen vacancies) in the bulk of the material. Grain and grain boundary conductivity evaluated from the impedance data revealed that Pr acts as a donor dopant for x ≤ 0.05 wt% while it is an acceptor for higher concentration, in accordance with XRD observations. Defect chemistry analysis for better interpretation of the acquired data is presented. Frequency and temperature dependent ac conductivity studies were also performed and the obtained activation energy values were associated with possible conduction mechanisms.

Flexible Magnetocaloric Fiber Mats for Room-Temperature Energy Applications.

Currently, magnetocaloric refrigeration technologies are emerging as ecofriendly and more energy-efficient alternatives to conventional expansion-compression systems. However, major challenges remain. A particular concern is the mechanical properties of magnetocaloric materials, namely, their fatigue under cycling and difficulty in processing and shaping. Nevertheless, in the past few years, using multistimuli thermodynamic cycles with multicaloric refrigerants has led to higher heat-pumping efficiencies. To address simultaneously the challenges and develop a multicaloric material, in this work, we have prepared magnetocaloric-based flexible composite mats composed of micrometric electroactive (EA) polyvinylidene fluoride (PVDF) fibers with embedded magnetocaloric/strictive La(Fe,Si)13 particles by the simple and cost-effective electrospinning technique. The composite's structural characterization, using X-ray diffraction (XRD) analysis, Fourier transform infrared (FTIR) spectroscopy, and measurements of the local-scale piezoresponse, revealed a cubic NaZn13-type structure of the La(Fe,Si)13 phase and the formation of the dominant polar ß-phase of the PVDF polymer. The PVDF-La(Fe,Si)13 composite showed an enhancement of the longitudinal piezoelectric coefficient (effective d33) (-11.01 pm/V) compared with the single PVDF fiber matrix (-9.36 pm/V). The main magnetic properties of La(Fe,Si)13 powder were retained in the PVDF-La(Fe,Si)13 composite, including its giant magnetocaloric effect. By retaining the unique magnetic properties of La(Fe,Si)13 embedded in the electroactive piezoelectric polymer fiber mats, we have designed a flexible, easily shapeable, and multifunctional composite enabling its potential application in multicaloric heat-pumping devices and other sensing and actuating devices.

Structural, magnetic, magnetocaloric and specific heat investigations on Mn doped PrCrO3 orthochromites.

We have synthesized PrCr0.85Mn0.15O3 (PCMO) chromite and investigated the influence of manganese (Mn) doping at Cr-sites on the structural, magnetic, magnetocaloric and thermal properties of PrCrO3 compound. No structural transition was observed with Mn substitution and the doped compound crystallized into distorted orthorhombic structure with Pnma space group which was confirmed by Rietveld refinement of x-ray powder diffraction patterns. Neel temperature, noticed at 168 K from the temperature variation of magnetization, smaller than that reported for PrCrO3, indicated the influence of Mn3+ substitution in decreasing the antiferromagnetic ordering. Magnetization was almost eight times higher than that reported for undoped sample. Magnetocaloric effect measured via the magnetic entropy change and relative cooling power demonstrated significant values in the temperature range 10-20 K. The values of magnetic entropy change are much superior to that reported for other polycrystalline orthochromites and even at smaller applied field strength. The material exhibited second order magnetic phase transition. The Debye temperature and the density of states at Fermi level were also calculated. The overall results make PrCr0.85Mn0.15O3 chromite a potential candidate to replace the existing materials for low temperature magnetic refrigeration.