Air-Stable and Eco-Friendly Symmetrical Imine with Thiadiazole Moieties in Neutral and Protonated form for Perovskite Photovoltaics.

This paper proposes molecular and supramolecular concepts for potential application in perovskite solar cells. New air-stable symmetrical imine, with thiadiazole moieties PPL2: (5E,6E)-N2,N5-bis(4-(diphenylamino)benzylidene)-1,3,4-thiadiazole-2,5-diamine), as a hole-transporting material was synthesised in a single-step reaction, starting with commercially available and relatively inexpensive reagents, resulting in a reduction in the cost of the final product compared to Spiro-OMeTAD. Moreover, camphorsulfonic acid (CSA) in both enantiomeric forms was used to change the HOMO-LUMO levels and electric properties of the investigated imine-forming complexes. Electric, optical, thermal, and structural studies of the imine and its complexes with CSA were carried out to characterise the new material. Imine and imine/CSA complexes were also characterised in depth by the proton Nuclear Magnetic Resonance 1H NMR method. The position of nitrogen in the thidiazole ring influences the basicity of donor centres, which results in protonation in the imine bond. Simple devices of ITO/imine (with or without CSA(-) or CSA(+))/Ag/ITO architecture were constructed, and a thermographic camera was used to find the defects in the created devices. Electric behaviour was also studied to demonstrate conductivity properties under the forward current. Finally, the electrical properties of imine and its protonated form with CSA were compared with Spiro-OMeTAD. In general, the analysis of thermal images showed a very similar response of the samples to the applied potential in terms of the homogeneity of the formed organic layer. The TGA analysis showed that the investigated imine exhibits good thermal stability in air and argon atmospheres.

Molecular Mobility in Oriented and Unoriented Membranes Based on Poly[2-(Aziridin-1-yl)ethanol].

Unoriented and oriented membranes based on dendronized polymers and copolymers obtained by chemical modification of poly[2-(aziridin-1-yl) ethanol] (PAZE) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate were considered. DSC, XRD, CP-MAS NMR and DETA, contribute to characterize the tendency to crystallize, the molecular mobility of the benzyloxy substituent, the dendritic liquid crystalline group and the clearing transition. The orientation of the mesogenic chain somewhat hindered this molecular motion, especially in the full substituted PAZE. The fragility, free volume and thermal expansion coefficients of these membranes near the glass transition are related to the orientation and the addition of the dendritic groups. PAZE-based membranes combine both order and mobility on a supramolecular and macroscopic level, controlled by the dendritic group and the thermal orientation, and open the possibility of preparing membranes with proper channel mobility that promotes selective ionic transport.

Research of Binary and Ternary Composites Based on Selected Aliphatic or Aliphatic-Aromatic Polymers, 5CB or SWCN Toward Biodegradable Electrodes.

The main goal of this paper was to study the optical, electrical, and thermal properties of hybrid composites based on biodegradable polymers (L,D-poly(lactic acid), polycaprolactone or Ecoflex®), single walled carbon nanotubes (SWCN), and 4'-pentyl-4-biphenylcarbonitrile (5CB). The biodegradable polymers' binary and ternary compositions were analyzed in detail by ultraviolet and visible (UV-Vis) spectroscopy taking into consideration their chemical structure and interactions with 5CB and SWCN. Differential scanning calorimetry (DSC) studies of the created hybrid layers showed thermal stability and changes in glass transition temperature and melting point in comparison to neat polymers, depending on the chemical structure of the polymer used and the type of composition. Morphology of the created layers were investigated by atomic force and polarizing microscopy. The static contact angle measurements of a water drop showed that all of the neat polymer layers were hydrophobic with angle values ranging from 108° to 115°. In addition, in the case of the Ecoflex layers, both with and without additives, a rapid sorption of the deposited water drop was observed. Finally, a simple device with poly(ethylene terephthalate) (PET)/indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/poly [[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl ]] (PTB7) : [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM)/Ag/biodegradable polymer:SWCN architecture was constructed and tested using an infrared (IR) thermographic camera to investigate the surface defects on the created hybrid layers. Increasing the SWCN admixture from 0.01 to 0.5% significantly improved the conductivity only in the case of L,D-poly(lactic acid):SWCN (10:0.5), for which above 5 V, a current with a resistance of 3030.7 Ω could be measured. In order to use the created layers as flexible electrodes, the first experiments were carried out with an admixture of SWCN and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) as conductive compounds.

Preparation and Characterization of Novel Polymer-Based Gel Electrolyte for Dye-Sensitized Solar Cells Based on poly(vinylidene fluoride-co-hexafluoropropylene) and poly(acrylonitrile-co-butadiene) or poly(dimethylsiloxane) bis(3-aminopropyl) Copolymers.

Polymer gel electrolytes based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and poly(acrylonitrile-co-butadiene) (PAB) or poly(dimethylsiloxane) bis(3-aminopropyl)-terminated (PDES-bAP) copolymers were prepared and investigated in dye-sensitized solar cells (DSSCs). Selected optical and electrochemical properties of all compositions with various ratio from 9:1 to 6:4 were investigated towards DSSC applications. The highest value of power conversion efficiency equal to 5.07% was found for DSSCs containing a PVDF-HPF:PAB (9:1) gel electrolyte. Compositions of electrolytes were additionally tested by electrochemical impedance spectroscopy. The influence of the ratio and type of polymers used as an additive to PVDF-HPF on absorption wavelengths, energy gap, and Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) levels were investigated. Individual components of DSSCs, such as the TiO2 layer and platinum nanoparticles, were imaged by scanning electron microscope. Finally, a DSSC module with six electrically separated solar cells with a 7 × 80 mm2 active area was constructed based on gel electrolytes and tested.

Selected Electrochemical Properties of 4,4'-((1E,1'E)-((1,2,4-Thiadiazole-3,5-diyl)bis(azaneylylidene))bis(methaneylylidene))bis(N,N-di-p-tolylaniline) towards Perovskite Solar Cells with 14.4% Efficiency.

Planar perovskite solar cells were fabricated on F-doped SnO2 (FTO) coated glass substrates, with 4,4'-((1E,1'E)-((1,2,4-thiadiazole-3,5-diyl)bis(azaneylylidene))bis(methaneylylidene))bis(N,N-di-p-tolylaniline) (bTAThDaz) as hole transport material. This imine was synthesized in one step reaction, starting from commercially available and relatively inexpensive reagents. Electrochemical, optical, electrical, thermal and structural studies including thermal images and current-voltage measurements of the full solar cell devices characterize the imine in details. HOMO-LUMO of bTAThDaz were investigated by cyclic voltammetry (CV) and energy-resolved electrochemical impedance spectroscopy (ER-EIS) and were found at -5.19 eV and -2.52 eV (CV) and at -5.5 eV and -2.3 eV (ER-EIS). The imine exhibited 5% weight loss at 156 °C. The electrical behavior and photovoltaic performance of the perovskite solar cell was examined for FTO/TiO2/perovskite/bTAThDaz/Ag device architecture. Constructed devices exhibited good time and air stability together with quite small effect of hysteresis. The observed solar conversion efficiency was 14.4%.

A comprehensive optical and electrical study of unsymmetrical imine with four thiophene rings and their binary and ternary compositions with PTB7 and PC70BM towards organic photovoltaics.

A new unsymmetrical imine with four thiophene rings was synthesized in a one-step reaction, starting from the commercially available and relatively inexpensive reagents. The obtained imine in the form of thin films exhibited photoluminescence properties in the 1.8-2.4 eV energy range and a photoluminescence lifetime of about 0.3 ns. The HOMO and LUMO levels of the imine determined by cyclic voltammetry were at about -5.19 eV and -3.05 eV, respectively. The density functional theory was applied to calculate the geometric and electronic structure of the imine. The UV-Vis spectra showed that the absorption range of the imine overlaps with that of PC70BM, and the absorption peak at the maximum of the imine at 424 nm is located between the two maxima at 404 nm and 461 nm of the fullerene derivative. The electron acceptor and donor activity of the imine was tested in the solar cell architecture: glass/ITO/PEDOT:PSS/active layer/In/Al. The best photovoltaic parameters, with very good reproducibility for each 8 pixels in the cell, were found for the active layer based on ternary mixture PTB7:PC70BM:imine at a weight ratio 8 : 13 : 1, with the power conversion efficiency of about 4%. The external quantum efficiency of devices with the imine was found to be about 40% at 3.3 eV. The thermal imaging together with the recorded current response at increasing potential showed that the presence of imine in the composition has a beneficial impact in terms of current flow stability at temperatures above 200 °C, compared to two component layers with the same imine as an additive.

UV-Vis Absorption Properties of New Aromatic Imines and Their Compositions with Poly({4,8-bis[(2-Ethylhexyl)oxy]Benzo[1,2-b:4,5-b']Dithiophene-2,6-diyl}{3-Fluoro-2-[(2-Ethylhexyl)Carbonyl]Thieno[3,4-b]Thiophenediyl}).

In this paper, four new aromatic imines containing at least one thiazole-based heterocycle were analyzed in detail by UV-Vis spectroscopy, taking into consideration their chemical structures and interactions with PTB7, a known polymeric electron donor widely used in bulk heterojunction organic solar cells. It is demonstrated that the absorption spectra of the investigated active compositions can be modified not only by changing the chemical structure of imine, but also via formulations with PTB7. For all investigated imines and PTB7:imine compositions, calibration curves were obtained in order to find the optimum concentration in the composition with PTB7 for expansion and optimization of absorption spectra. All imines and PTB7:imine compositions were investigated in 1,2-dichlorobenzene by UV-Vis spectroscopy in various concentrations, monitoring the changes in the π-π* and n-π* transitions. With increasing imine concentrations, we did not observe changes in absorption maxima, while with increasing imine concentrations, a hypochromic effect was observed. Finally, we could conclude that all investigated compositions exhibited wide absorptions of up to 800 nm and isosbestic points in the range of 440-540 nm, confirming changes in the macromolecular organization of the tested compounds. The theoretical calculations of their vibration spectra (FTIR) and LUMO-HOMO levels by Density Functional Theory (DFT) methods are also provided. Finally, IR thermal images were measured for organic devices based on imines and the imine:PTB7 composite.

Dielectric, Thermal and Mechanical Properties of l,d-Poly(Lactic Acid) Modified by 4'-Pentyl-4-Biphenylcarbonitrile and Single Walled Carbon Nanotube.

We report here the preparation and thermal, electrical and mechanical characterization of binary and ternary films based on l,d-poly(lactic acid) (l,d-PLA) and 4'-pentyl-4-biphenylcarbonitrile (5CB) and Single Walled Carbon Nanotubes (SWCN) with various weight ratio. The transitions for all investigated hybrid compositions detected by differential scanning calorimetry method were shifted to lower temperatures with increasing the concentration of 5CB in the mixture with polymer. Frequency domain dielectric spectroscopy method and thermal imaging together with polarized optical microscope were used to study electric and structural properties of created hybrid compositions. The best electrical conductivity was observed for hybrid composite l,d-PLA:5CB:SWCN with ratio 10:1:0.5 w/w/w - resistance of 41.0 Ω and thermal response up to 160 °C without causing any damages. Films in crystal form are much more inflexible than in amorphous and can be explain by the cold crystallization occurs at heating while the materials changed their physical state. The value of ε' increases with increasing the 5CB admixture. Moreover, the addition of 5CB to l,d-PLA resulted in increased flexibility of polymeric base films. The best material flexibility and short-term strength were obtained for l,d-PLA sample with 9% 5CB content.

Influence of TiO2 Nanoparticles on Liquid Crystalline, Structural and Electrochemical Properties of (8Z)-N-(4-((Z)-(4-pentylphenylimino)methyl)benzylidene)-4-pentylbenzenamine.

Organic-inorganic hybrids based on liquid crystalline symmetrical imine (8Z)-N-(4-((Z)-(4-pentylphenylimino)methyl)benzylidene)-4-pentylbenzenamine (AZJ1) with two aliphatic chains and TiO2 nanomaterials were obtained and investigated taking into account thr crystallographic form of titanium dioxide i.e., anatase versus rutile. The type of TiO2 influences the mesomorphic properties of imine AZJ1, as observed by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) techniques. Fourier-Transform Infrared Spectroscopy (FT-IR) was used to investigate the interactions of oxygen vacancies located on the TiO2 surface with the studied AZJ1 imine together with studying the influence of temperature. Both imine:TiO2 anatase versus rutile hybrids possessed the highest occupied molecular orbital (HOMO) levels of about -5.39 eV (AZJ1:anatase) and -5.33 eV (AZJ1:rutile) and the lowest unoccupied molecular orbital (LUMO) levels of about -2.24 eV. The presence of TiO2 in each hybrid did not strongly affect the redox properties of imine AZJ1. Organic devices with the configuration of ITO/TiO2/AZJ1 (or AZJ1:TiO2 anatase versus rutile)/Au were fabricated and investigated in the presence and absence of visible light irradiation with a light intensity of 93 mW/cm². Finally, to analyze defects in the constructed organic devices we used thermal imaging and atomic force microscopy (AFM). The addition of TiO2 in both crystallographic forms has a positive influence on layer-forming properties that manifests itself as a very homogenous heat distribution for the whole sample.

Solvent-free thiophene-based electrolytes: synthesis of new liquid-crystalline ionic conductors for batteries: part I.

New liquid crystalline thiophene esters, thiophene-3-yl 3,4,5-tris(n-dodecan-1-yloxy)benzoate (ThBz1) and thiophene-3-yl 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate (ThBz2), were synthesized for use in lithium-ion batteries as safe, new solvent-free ionic conductors. Both compounds were synthesized in multi-step reactions and were characterized via1H, 13C NMR and FT-IR spectroscopy, confirming the formation of the desired products. ThBz1 and ThBz2 showed good thermal stability and liquid crystalline behaviour. Electrochemical tests demonstrated a wide electrochemical window of 4 V for both tested ThBz compounds. Moreover, preliminary battery tests for new electrolytes in the LiCoO2/Li4Ti5O12 system confirmed their applicability in lithium-ion batteries.

Structural and electrochemical studies of TiO2 complexes with (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivative bases towards organic devices.

Three (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivatives were synthesized via a condensation reaction with p-toluenesulfonic acid as a catalyst. The effects of the end groups and vinylene (-HC[double bond, length as m-dash]CH-) moieties on the structural, thermal, optical, electrochemical and photovoltaic properties of imines were investigated to check the influence of TiO2 on the imine properties. The thermal behavior of imines and their complexes with TiO2 was widely investigated using FT-IR, XRD, DSC and POM methods in order to determine the order type in the imine structure. All imines present the highest occupied molecular orbital (HOMO) levels of about -5.39 eV (SAI1 and SAI2) and -5.27 eV (SAI3) and the lowest unoccupied molecular orbital (LUMO) levels at about -3.17 eV. The difference of the end groups in the imines in each case did not affect redox properties. Generally, both oxidation and reduction are easier after TiO2 addition and it also changes the HOMO-LUMO levels of imines. Moreover, changes in the characteristic bands for imines in the region 1500-1700 cm-1 observed as a drastic decrease of intensity or even disappearance of bands in the imine : TiO2 mixture suggest the formation of a complex (C[double bond, length as m-dash]N)-TiO2. Organic devices with the configuration of ITO/TiO2/SAIx (or SAIx : TiO2)/Au were fabricated and investigated in the presence and absence of visible light irradiation with an intensity of 93 mW cm-2. In all imines and complexes with TiO2, the generation of the photocurrent indicates their use as photodiodes and the best result was observed for SAI3 : TiO2 complexes.

Synthesis and characterization of two new TiO2-containing benzothiazole-based imine composites for organic device applications.

The effect of the presence of titanium dioxide in two new imines, (E,E)-(butane-1,4-diyl)bis(oxybutane-4,1-diyl) bis(4-{[(benzo[d][1,3]thiazol-2-yl)methylidene]amino}benzoate) (SP1) and (E)-N-[(benzo[d][1,3]thiazol-2-yl)methylidene]-4-dodecylaniline (SP2), on the properties and stability of imine:TiO2 composites for organic device applications were examined. The investigated titanium dioxide (in anatase form, obtained via the sol-gel method) exhibited a surface area of 59.5 m2/g according to Brunauer-Emmett-Teller theory, and its structure is a combination of both meso- and microporous. The average pore diameter calculated by the Barrett-Joyner-Halenda method was 6.2 nm and the cumulative volume of pores was 0.117 m3/g. The imine SP1 exhibited columnar organization (Col), while SP2 revealed a hexagonal columnar crystalline phase (Colhk). The imine:TiO2 mixtures in various weight ratio (3:0, 3:1, 3:2, 3:3) showed a lower energy gap and HOMO-LUMO energy levels compared to pure TiO2. This implies that TiO2 provides not only a larger surface area for sensitizer adsorption and good electron collection, but also causes a shift of the imine energy levels resulting from intermolecular interaction. Also the temperature of the phase transition was slightly affected with the increase of TiO2 concentration in imine-based composites. The changes observed in the Fourier transform middle-infrared absorption (FT-MIR) spectra confirmed the significant influence of TiO2 on structural properties of both investigated imines. Similar interactions of oxygen vacancies existing on the TiO2 surface with SP1 and SP2 were observed. The imine:TiO2 mixtures showed good air stability and reusability, which demonstrates its potential for organic device applications.

In Situ Raman Spectroscopy as a Tool for Structural Insight into Cation Non-Ionomeric Polymer Interactions during Ion Transport.

Low-modified liquid-crystalline polyether (CP36), as a model compound, was synthesised with the purpose of preparing a membrane with columnar ionic channels. A free-standing cation permselective biomimetic membrane was successfully prepared and found to have channels made of polymeric columns homeotropically oriented, which was confirmed in X-ray diffraction (XRD) analysis. A first insight into a real-time interaction between two selected cations: H⁺ and Na⁺, and polyether during transport through the polymeric membrane was demonstrated using joined chronoamperometry and Raman spectroscopy techniques. Raman studies unveiled the possibility for smaller protons to bypass the usual ionic pathway via polyetheric chain and use outer part of ionic channel for conduction thanks to ester bonds.

Hybrid Materials Based on l,d-Poly(lactic acid) and Single-Walled Carbon Nanotubes as Flexible Substrate for Organic Devices.

We report on the application of l,d-poly(lactic acid) (l,d-PLA) with dispersed Single-Walled Carbon Nanotubes (SWCN) as a flexible translucent electrode for organic devices. We used commercially available nanotubes in various weight ratios from 0 to 8% dispersed in chloroform polymeric solution by ultrasonication and were drop cast. The created hybrid materials were investigated by differential scanning calorimetry to determine the influence of SWCN content on the thermal behavior, while polarizing optical microscope was used to find the effect of mechanical deformations on the textures. Drop-cast films were studied by optical transmittance, conductivity, dielectric properties and by thermal imaging under applied potential. Thermal imaging provided evidence of visible voltage-activated conduction. Simple mechanical deformation such as bending with stretching at edge to ca. 90 and elongation test were performed. Moreover, interactions between l,d-poly(lactic acid) and SWCN were investigated by FT-IR and NMR spectroscopy. Finally, we can conclude that the thermographic examination of created films permits fast, simple and inexpensive localization of defects on the surface of l,d-PLA:SWCN film, together with the electrical properties of the films.

Preparation and characterization of light-sensitive microcapsules based on a liquid crystalline polyester.

Photosensitive microcapsules and membranes based on poly(α-methylstilbenesebacoate-co-α-methylstilbeneisophthalate), containing the photosensitive α-methylstilbene moiety, were prepared by a phase-inversion precipitation process. In order to simulate the morphology and behavior of the microcapsule shell under UV irradiation, an exhaustive characterization of a membrane was first performed by ESEM, POM, AFM, and contact angle measurements. The prepared microcapsules contained either chloroform or a concentrated solution of vanillin in chloroform as the core; in all cases, before UV irradiation, their outer surface appeared smooth and dense. The influence of vanillin on microcapsule cross-section morphology was observed by ESEM microscopy. Release of vanillin in water, at room temperature, was markedly influenced by UV irradiation: in the absence of irradiation, it was practically negligible, while when microcapsules were submitted to continuous irradiation with UV light, the surface morphology of the capsules changed drastically and vanillin started to be released after ca. 20 min of irradiation.