Effect of long alkyl chains of aniline donor on the photovoltaic performance of D‐π‐A zinc porphyrin for dye‐sensitized solar cells

Three novel dyes of JJ1 , JJ2 , and JJ6 featured zinc porphyrin as a basic core structure; N, N‐alkyl‐4‐(prop‐1‐yn‐1‐yl)aniline as an electron donor linked to meso‐10‐position; 4‐(prop‐1‐yn‐1‐yl)benzoic acid as an electron acceptor linked to meso‐20‐position; and 2,6‐bis(dodecyloxy)phenyl or 2,6‐bis(octyloxy)phenyl respectively linked to meso‐5 and meso‐15‐positions of zinc porphyrin have been synthesized and used for dye‐sensitized solar cells. Porphyrin JJ6 featured the shortest alkyl group (─C₄H₉) on the donor, whereas JJ2 contained the longest alkyl groups (─C₁₂H₂₅), and JJ1 has a medium length of octyl groups. With these new porphyrin sensitizers, we observed that JJ6 has 7.55% power conversion efficiency under simulated one‐sun illumination (AM 1.5 G, 100 mW/cm²) with J_SC = 18.64 mA/cm², V_OC = 0.66 V, and fill factor (FF) = 0.61, which was higher than the other two; JJ1 (7.35%) with J_SC = 18.83 mA/cm², V_OC = 0.68 V, and FF = 0.60; and JJ2 (6.33%) with J_SC = 15.69 mA/cm², V_OC = 0.62 V, and FF = 0.65. The power conversion efficiency of JJ6 and JJ1 were higher than JJ2 , demonstrating that the lengthy alkyl groups on the aniline cause a decrease in efficiency of the devices.     

Effects of alkyl side chains positioning and presence of fused aromatic units in the backbone of low‐bandgap diketopyrrolopyrrole copolymers on the optoelectronic properties of organic solar cells

The systematic optimization of the chemical structure of low‐bandgap (LBG) donor‐acceptor polymeric semiconductors is a challenging task for which accurate guidelines are yet to be determined. Several different structural and molecular parameters are crucial ingredients for obtaining LBG polymers that simultaneously possess high power conversion efficiencies, good processability in common organic solvents, and enhanced stability in organic photovoltaic devices. In this work, we present an extensive structure–optoelectronic properties–solar cell performance study on the emerging class of diketopyrrolopyrrole‐based LBG polymers. In particular, we investigate alkyl side chain positioning by introducing linear alkyl side chains into two different positions (α‐ and β‐), and the distance of the electron rich and electron deficient monomers within the repeat units of the polymer chain. We demonstrate that anchoring linear alkyl side chains to the α‐positions and introducing fused moieties into the polymer backbone, can be beneficial toward maintaining photocurrents similar to the unsubstituted derivative, and concurrently exhibit better processabiliy in common organic solvents. These results can provide a design rationale towards further optimization of semiconducting polymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 138–146     

Tetrazole thiolate/disulfide organic redox couples carrying long alkyl groups in dye-sensitized solar cells with Pt-free electrodes

Colorless tetrazole thiolate/sulfide redox couples carrying long alkyl groups, such as n-butyl, n-hexyl, and n-octyl groups, were synthesized as electrolytes in iodine/iodide-free dye-sensitized solar cells (DSSCs). Among N719/TiO₂-based DSSCs employing these highly soluble redox couples for 3-methoxypropionitrile (3-MPN) and ionic liquid with PEDOT counter electrode, the DSSC with n-hexyl redox analogue gave an optimized η value of 4.32%. An observed respectable quantum efficiency for 400–500 nm light is in sharp contrast to the decreased performance for iodine/iodide systems that originates from the substantial light absorption of iodine. On the other hand, the redox possessing n-octyl group significantly lowered the cell performance, which could be a result of the much increased resistance of electrolyte diffusion in the DSSC.     

Effects of processing additives in non-fullerene organic bulk heterojunction solar cells with efficiency >11%

The solar cell surface morphologies with different additives observed with slightly changed in roughness. It is easily to get the best PCE of 11.1% with using 0.5% DIO additives.     

Synthesis of the (X-DADAD)n-type conjugated polymers with 2,1,3-benzoxadiazole acceptor blocks and their application in organic solar cells

Two polymers with benzoxadiazole acceptor units were synthesized and investigated as electron donor materials in organic solar cells. Variation of the alkyl substituents was shown to significantly affect the optoelectronic properties of the polymers. In particular, the polymer HOMO energy level was lowered by 0.1 eV, while maintaining the same band gap, by replacement of the 2-ethylhexyl side-chains with the 2-hexyldecyl group. This modification also resulted in a higher open circuit voltage of the solar cells.     

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     

Polymerizable C70 derivatives with acrylate functionality for efficient and stable solar cells

Fullerene-based organic solar cells are generally suffering from severe microstructure evolution occurring in their bulk heterojunction active layers and thus are extremely stable. To address it, four polymerizable C₇₀ fullerene derivatives, [6,6]-phenyl-C₇₁-ethyl acrylate (PC₇₁EA), [6,6]-phenyl-C₇₁-propyl acrylate (PC₇₁PrA), [6,6]-phenyl-C₇₁-butyl acrylate (PC₇₁BA), and [6,6]-phenyl-C₇₁-pentyl acrylate (PC₇₁PeA), have been designed, synthesized, and investigated. These fullerene compounds have a molecular structure, shape and size very like the conventional C₇₀ fullerene acceptor, [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), and have been found no different in their light absorption, redox potentials, and frontier orbital energy levels. Using these fullerene acrylates individually as acceptor and poly(3-hexylthiophene) as donor, organic solar cells have been fabricated and gave optimal efficiencies ranging from 3.32% to 4.16%, comparable to PC₇₁BM-based reference cells (4.06%). Owing to their acrylate functionality, these fullerene derivatives can turn into insoluble upon heating, and thus endow their solar cell devices much better thermostability than PC₇₁BM-based reference cells. The best one, coming from PC₇₁PeA devices, reported an optimal efficiency of 4.16%, and maintained 91.7% efficiency after heat treatment at 150 °C for 35 h. As a sharp contrast, the PC₇₁BM reference cell dropped its optimal efficiency from 4.06% to 0.48% only after 5 h heat treatment. X-ray diffraction, optical and atomic force microscopy, and space-charge-limited current method have been carried out to understand active layer structure, morphology, and charge mobility change during heat treatment.     

2,3‐bis(5‐Hexylthiophen‐2‐yl)‐6,7‐bis(octyloxy)‐5,8‐di(thiophen‐2‐yl) quinoxaline: A good construction block with adjustable role in the donor‐π‐acceptor system for bulk‐heterojunction solar cells

Three 2,3‐bis(5‐hexylthiophen‐2‐yl)‐6,7‐bis(octyloxy)‐5,8‐di(thiophen‐2‐yl)‐quinoxaline ( BTTQ )‐based conjugated polymers, namely, PF‐BTTQ ( P1 ), PP‐BTTQ ( P2 ), and PDCP‐BTTQ ( P3 ), were successfully synthesized for efficient polymer solar cells (PSCs) with electron‐rich units of fluorene and dialkoxybenzene and electron‐deficient unit dicyanobenzene, respectively. All the polymers exhibited good solubility in common organic solvents and good thermal stability. Their deep‐lying HOMO energy levels enabled them good stability in the air and the relatively low HOMO energy level assured a higher open circuit potential when used in PSCs. Bulk‐heterojunction solar cells were fabricated using these copolymers blended with a fullerene derivative as an acceptor. All of them exhibited promising performance, and the best device performance with power conversion efficiency up to 3.30% was achieved under one sun of AM 1.5 solar simulator illumination (100 mW/cm²). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012