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Due to its high electron affinity and electron mobility in a wide absorption range of the visible solar spectrum, [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) is often used as an efficient acceptor in organic photovoltaics. In turn, imines are additives to the active layer of organic solar cells, mainly due to the free electron pair of the imine nitrogen atom and the presence of various chemical groups affecting the polarity and conformations of molecules. However, the attainable efficiency is not as high as expected. Therefore, we have systematically investigated two imines and their mixtures with PC71BM by spectroscopic (the high pressure UV–Vis and frequency domain dielectric), thermoelectric, and mechanical methods for organic, flexible photovoltaics. Both the imines, (N,NʹE,N,NʹE)-N,Nʹ-([2,2ʹ:5ʹ,2ʺ-terthiophene]-5,5ʺ-diylbis(methanylylidene))bis(benzo[d]thiazol-2-imine) (SC3) and (6E)-N-((5-(5-(5-((E)-(4-(4-(4-fluorophenyl)thiazol-2-yl)phenylimino)methyl)thiophen-2-yl)thiophen-2-yl)thiophen-2-yl)methylene)-4-(4-(4-fluorophenyl)thiazol-2-yl)benzenamine (SC13), have the same core composed of three thiophene rings but different terminal chains of the molecules. In the imine SC3, the imine bond is followed by benzothiazole rings on both sides of the core, while in SC13, a thiazole ring separates two benzene rings, the terminal one F-substituted. The difference in molecular structure affects the electric properties of the neat imine and its mixed layers. An addition of PC71BM to the imines improves their electric conductivity. The mechanical studies focused on the stress at break and elongation showed superior behaviour compared to fullerene derivative. High pressure systematically reduces the band gap energy, Eg, from 1.68 eV at 0.16 GPa to 1.51 eV at 2.69 GPa for PC71BM, from 1.77 eV at 0.1 MPa to 1.53 eV at 4.15 GPa for SC3, and from 1.99 eV at 0.11 GPa to 1.8 eV at 3.10 GPa for SC13, as determined by the UV–Vis absorbance measurements in a diamond-anvil cell. These Eg reductions reflect the compressed intermolecular interactions that can be used to monitor the structural stability of these compounds. Based on the dielectric studies it was found that the relaxation processes registered for both imines are probably the grain boundary relaxation. Two processes also appear in the systems with PC71BM, but none of them is the one characteristic of imines. The high-frequency process has a dipole character while the low-frequency one is probably the grain boundary relaxation of these systems. The mechanism of quasi-DC conduction in various temperature ranges in the studied systems was also determined. [ABSTRACT FROM AUTHOR]

• We synthesized three imines with triphenylamine or terthiophene core. • We analyse photovoltaic properties in the level of symmetry of imines, presence of DIO, DPE, PFN. • The J-V effects depend on the chemical structure of imine and presence of additives. • Organic solar cells containing PV-BLJ-SC2 imine and PTB7:PC 71 BM:DIO showed the efficiency increased by more than 107 % compared with reference device lack of imine. • We presents a quite effective and cheap method to improve the efficiency of organic solar cells by adopting a ternary approach. In this paper the influence of imine symmetry and triphenylamine moieties presence on photovoltaic properties of bulk heterojunction organic solar cells were analysed in details. Three imines: (E)-N-(4-((4-((E)-(benzo[d]thiazol-2-ylimino)methyl)phenyl)(phenyl)amino)benzylidene)benzo[d]thiazol-2-imine (PV-BLJ-SC1), (E)-N-(4-diphenylamino)benzylidene)benzo[d]thiazol-2-imine (PV-BLJ-SC2) and (N,N'E,N,N'E)-N,N'-([2,2′:5′,2′'-terthiophene]-5,5′'-diylbis(methanylylidene))bis(benzo[d]thiazol-2-imine) (PV-BLJ-SC3) were investigated as donor or acceptor components in binary and ternary active layer. Moreover, the influence of admixture (1,8-diiodooctane or diphenyl ether), and presence of poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9–dioctylfluorene)] as cathode buffer layer on the photovoltaic parameters of the constructed imine-containing solar cells was analysed in details. All the conducted experiments confirmed the possibility of using unsymmetrical imine PV-BLJ-SC2, showing the best results, in organic photovoltaics. The HOMO and LUMO levels of the imines were determined by cyclic voltammetry, showing dependance of on the chemical structure and its symmetry, and for PV-BLJ-SC2 gaved −5.07 eV and −2.23 eV, respectively. In the case of PV-BLJ-SC1 and PV-BLJ-SC2 the electron density of HOMO was mainly located on triphenylamine moieties, while in the case of PV-BLJ-SC3 on thiophene moieties, as it was confirmed by the density functional theory studies. Based on the highest conductivity (9 × 10-8 S/cm2) result for PV-BLJ-SC2, this imine was selected to prepare binary and ternary layers with PTB7 or PTB7:PC 71 BM and thermal imaging studies were performed. Finally, PV-BLJ-SC2 was introduced to the PTB7:PC 71 BM binary system, where a power conversion efficiency as high as 4.17% was achieved after the addition of 1,8-diiodooctane. It gaved better result than the reference sample containing PTB7:PC 71 BM and 1,8-diiodooctane (3.11%). In the case of reference solar cells the addition of 1,8-diiodooctane improved the efficiency of about 22 %, while for solar cells containing also PV-BLJ-SC2 imine the efficiency increased by more than 107 %. Our study presents a quite effective and cheap method to improve the efficiency of organic solar cells by adopting a ternary approach. [ABSTRACT FROM AUTHOR]

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=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=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. [ABSTRACT FROM AUTHOR]

Two bent-shaped imines (9E)-N-(3-((E)-(4-hexadecylphenylimino)methyl)benzylidene)-4-hexadecylbenzenamine (SL1) and (10E)-N-(3-((E)-(4-(perfluorooctyl)phenylimino)methyl)benzylidene)-4-(perfluorooctyl)benzenamine (SL2) were prepared by condensation reaction in N,N-dimethylacetamide to study their thermal, structural and electrochemical properties, as well as their mixtures with titanium dioxide. Chemical structure, temperature and TiO2 influences on the phase transition temperatures, enthalpy, texture and molecular dynamics of both imines were investigated by differential scanning calorimetry, polarising optical microscopy and Fourier transform middle-infrared absorption spectroscopy during heating and cooling. Changes in the surface morphology of the imines and their mixtures with TiO2 were registered by atomic force microscopy. X-ray study showed the tendency to form lamellas in the case of SL2 as an effect of the presence of two terminal perfluorinated alkyl chains connected to a polar mobile aromatic core, which resulted in microsegregation. Additionally, TiO2 influences the energy gap and HOMO-LUMO levels of imines as was detected by cyclic voltammetry. Finally, devices with two types of architectures, such as ITO/TiO2/SL1(or P3HT)/Au and ITO/TiO2/SL1:P3HT/Au were constructed and investigated under irradiation intensity of 97.7 mW/cm2. [ABSTRACT FROM AUTHOR]

A new piperazine imine, (7E)-N-((4-((E)-(4-hexadecylphenylimino)methyl) piperazin-1-yl)methylene)-4-dodecylbenzenamine, has been synthesized by the condensation of 1,4-piperazinedicarboxaldehyde with 4- hexadecylaniline. The imine was characterized by cyclic voltammetry, Fourier transform middle-infrared absorption spectroscopy and X-ray diffraction. Thermal properties of imine was analyzed by differential scanning calorimetry method during first and second heating scan at 10 and 20 °C/min. Texture of imine was investigated by polarized optical microscopy and atomic force microscopy. Furthermore, imine was blended with titanium dioxide in anatase form and fully characterized by the same methods. Piperazine imine and its mixture with titanium dioxide exhibited only a transition from crystal to isotropic state. Imine exhibits two-step reduction wave attributed to one-electron transfer in each step as was found by cyclic voltammetry. Both titanium dioxide and poly(3-hexylthiophene) change the electrochemical properties of piperazine imine, however, in different ways. Studied imine blended with titanium dioxide exhibited higher value of energy band gap than pure piperazine imine and lower Eg than pure poly(3-hexylthiophene). [ABSTRACT FROM AUTHOR]

The crystal structure was determined for the first time for 4-[(di-p-tolyl-amino)benzylidene]-(5-pyridin-4-yl-[1,3,4]thiadiazol-2-yl)-imine (trans-PPL9) by X-ray diffraction. The imine crystallized in the monoclinic P21/n space group with a = 18.9567(7) Å, b = 6.18597(17) Å, c = 22.5897(7) Å, and β = 114.009(4)°. Intermolecular interactions in the PPL9 crystal were only weak C−H⋯N hydrogen bonds investigated using the Hirshfeld surface. The electronic and geometric structure of the imine were investigated by the density functional theory and the time-dependent density-functional theory. The properties of the imine in neutral and protonated form with camforosulphonic acid (CSA) were investigated using cyclic voltammetry, UV–vis and 1H NMR spectroscopy. Theoretical and experimental studies showed that for the 1:1 molar ratio the protonation occured on nitrogen in pyridine in the PPL9 structure, as an effect of Brönsted acid–base interactions. Thermographic camera was used to defined defects in constructed simple devices with ITO/PPL9 (or PPL9:CSA)/Ag/ITO architecture. In conclusion, a thermally stable imine was synthesized in crystalline form and by CSA doping, a modification of absorption spectra together with reduction of overheating process was observed, suggesting its potential application in optoelectronics. [ABSTRACT FROM AUTHOR]

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%. [ABSTRACT FROM AUTHOR]

In this study new symmetrical and unsymmetrical imines based on 4-[4-(4-fluorophenyl)1,3-thiazol-2-yl]aniline and 2,2′,5′,2"-terthiophene-5,5"-dicarboxaldehyde or 2,2':5′, 2"-terthiophene-5-carboxaldehyde, respectively, were synthesized by melt condensation with the yield of 86% and 40%. The 5% weight loss of the imines was found in temperature range from 294 to 390 °C in nitrogen, depending on the symmetry of aldehyde used in synthesis. The band gap of symmetrical imine (PV-BLJ-SC13) is lower by about ∼0.33 eV than that of unsymmetrical PV-BLJ-SC14. For both imines the electron density of HOMO level is mainly located on thiophene moieties and is extended to imine bonds in thiazole rings and imine moieties. The theoretical calculations of their HOMO-LUMO levels by DFT methods were also provided. The UV–Vis absorption spectra and cyclic voltammograms of imines both in the form of thin films cast on the electrode as well as dissolved in 1,2-dichloromethane were studied to determine the electrochemical and optical band gap energies as well as correlate the positions of HOMO and LUMO levels obtained by DFT and electrochemical methods. The resistance of imines was approximately 113.8 Ω and 102.4 Ω for PV-BLJ-SC13 and PV-BLJ-SC14, respectively as determined by IR thermal images and have a tendency to decrease by about 17–24 Ω when mixed with PTB7 and PC 71 BM. Both imines showed very bright luminescence. Moreover, optical absorption, photoluminescence and IR thermal images were measured for imine:PTB7 or imine:PTB7:PC 71 BM composite. Finally, simple organic solar cells based on (PTB7:imine):PC 71 BM in weight ratio (4:1):8 and (8:1):13 w/w were constructed and characterized. The highest power conversion efficiency, which was equal to 0.42% was determined for the ITO/PEDOT:PSS/PTB7:PV-BLJ-SC13:PC 71 BM (4:1):8/Al device. In addition, the power conversion efficiency was strongly dependent on the weight ratio of imine in active layer. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Three C 70 fullerene derivatives, namely, C70-BTB and C70-MTB with thiophene or C70-MTP thiophene and pyrrolidyne moieties were synthesized and compared with synthesized C70-IPH containing indene moieties. Moreover, C70-BTB was compared with C60-BTB to analyse in deep the influence of fullerene football and rugby balls on the selected opto-electrical properties of new fullerene derivatives. All fullerene derivatives were characterized theoretically by using both time-dependent and independent density functional theory with the Perdew-Burke-Ernzerhof and Becke-Lee, W. Yang, R.G. Parr. The energy levels of the highest occupied molecular orbitals (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs) were calculated and compared with corresponding values determined experimentally by cyclic voltammetry (CV). It was found that the LUMO HOMO energy gaps determined by the DFT/B3LYP/6–31G(d) method agree very precisely with the corresponding values obtained in the CV experiments. For the first time a possibility of electropolymeryzation of C60-MTB C70-BTB, C70-MTB and C70-MTP with (E)-1-([2,2′:5′,2′'- terthiophen ]-5-yl)-N-{4-[4-(4- fluorophenyl)-1,3- thiazol -2- yl ]phenyl}methanimine (PV-BLJ-SC14) was shown. All fullerene derivatives and blends with poly(3-hexylthiophene-2,5-diyl) and poly(4,8-bis[(2- ethylhexyl) oxy ]benzo[1,2- b :4,5- b ′]dithiophene-2,6-diyl-alt-3-fluoro-2-[(2- ethylhexyl) carbonyl ]thieno[3,4- b ]thiophene-4,6-diyl) were investigated in deep by UV–Vis spectroscopy in the solution and as the solid layers together with photoluminescence spectra. Structural defects of created layers based on new fullerene derivatives were studied by atomic force microscopy and thermal imaging. To summarize, the investigated fullerene derivatives present much better electrical properties than widely used PC 70 BM. Moreover, the indene and pyrrolidine modifications demonstrated the best stability (thermally and at passing current) and electrical performance for all tested modifications. Additionally, a possible molecule rearrangement was observed resulting in improvement of electric conductivity through the layer. Finally, simple bulk-heterojunction polymer solar cells were constructed based on new fullerene derivatives as acceptors. [ABSTRACT FROM AUTHOR]