Effect of co‐solvents on the photovoltaic performance of an inverted organic solar cell

We investigated the effect of varying polymer crystallinity, morphology, and optical property, produced by adding four different co‐solvents in to the poly(3‐hexylthiophene) (P3HT): [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) active layer blend solution, on the functioning of an inverted polymeric solar device. Photovoltaic devices primed with cyclohexanone co‐solvent showed the best performance with power conversion efficiency (PCE) reaching a value of 3.01 ± 0.04%. Improvement in efficiency is related to an increase in photocurrent which is due to a combined result of ordered P3HT crystallite growth, as well as of the precise size and phase separation of domains. POLYM. ENG. SCI., 55:1382–1388, 2015. © 2015 Society of Plastics Engineers     

Effect of the regioregularity of poly(3‐hexylthiophene) on the performances of organic photovoltaic devices

BACKGROUND: The highest efficiencies of bulk‐heterojunction solar cells from poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) reported so far are close to 6%. Phenomena occurring during the photovoltaic process, such as the creation, diffusion and separation of excitons, as well as charge carrier transport, are governed by the active layer morphology. The latter phenomenon, which depends on the self‐organization of P3HT, can be influenced by its degree of regioregularity. The aim of this work is to clarify the relationship between the regioregularity of P3HT, the composition of P3HT/PCBM blends and the performances of photovoltaic devices. RESULTS: Two types of P3HTs with different degrees of regioregularity have been synthesized and used as active layers with PCBM in photovoltaic cells. The higher performances in photovoltaic devices are obtained for high‐regioregular P3HT and can be explained considering the self‐organizing properties of high‐regioregular P3HT, leading to higher sunlight absorption and higher hole mobilities. In addition, this report demonstrates the importance of the ratio of P3HT versus PCBM in correlation with the regioregularity of P3HT on the optical properties, charge transport and characteristics of photovoltaic cells. CONCLUSION: We have investigated the dependence of the photovoltaic properties of P3HT/PCBM blend‐based photovoltaic devices on the degree of regioregularity of P3HT. We find that the best performance is exhibited by devices based on highly regioregular P3HT. Also, the best performances are not obtained for the same P3HT:PCBM weight ratios for high‐regioregular P3HT (1:0.8) and low‐regioregular P3HT (1:3). Copyright © 2007 Society of Chemical Industry     

Solvent effects on gravure-printed organic layers of nanoscale thickness for organic solar cells

The effects of different solvents on the fabrication of organic photovoltaic cells by gravure printing are reported. Polymer bulk heterojunction solar cells were fabricated with ITO/PEDOT: PSS/P3HT: PCBM/Al layer structures using 4–9 wt% mixtures of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) in 1,2-dichlorobenzene to optimize solution viscosity for gravure printing. 7 wt% P3HT: PCBM showed optimal efficiency of 1.64% and resulted in an active layer 340 nm thick. Three solvents, 1,2-dichlorobenzene, chloroform, and chlorobenzene, were tested and a 1: 1 ratio mixture of 1,2-dichlorobenzene and chloroform resulted in the best efficiency of 2.21%. This study demonstrates the importance of solvent effects in the gravure printing of organic photovoltaic devices.     

Towards optimization of functionalized single-walled carbon nanotubes adhering with poly(3-hexylthiophene) for highly efficient polymer solar cells

In this paper, we present the optimization of single-walled carbon nanotubes (SWCNTs) by acid-treatment, solution ultrasonication time and dispersion in photoactive layer for efficient organic solar cells. After non-covalently adhering with poly(3-hexylthiophene) (P3HT), pre-functionalized SWCNTs were blended into the composites of P3HT and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as photoactive layer, and a maximum power conversion efficiency (PCE) of 3.02% with a short-circuit current density of 11.46 mA/cm² was obtained from photovoltaic cell indium-tin oxide (ITO)/poly(ethylene-dioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)/P3HT:PCBM:SWCNTs/Al with an optimum 0.3 wt% SWCNTs in P3HT:PCBM:SWCNTs nanocomposite, the PCE can be enhanced by more than 10% as compared to the control device ITO/PEDOT:PSS/P3HT:PCBM/Al. The performance improvement by incorporating with functionalized SWCNTs is mainly attributed to the extension of excitons dissociation area and fastening charge carriers transfer across the active layer.     

Enhanced Thermal Stability of Inverted Polymer Solar Cells with Pentacene

In this study, we focused on the thermal stability of organic solar cells based on poly(3-hexylthiophene) (P3HT) and (6,6)-phenyl C₆₁-butyric acid methyl ester (PCBM), fabricated by blends of P3HT : PCBM : pentacene. Enhanced thermal stability of organic solar cells was achieved by introducing pentacene (Pc) into blends of P3HT : PCBM in organic solar cells with the structure indium tin oxide/ZnO/P3HT : PCBM : Pc/poly(3,4-ethylenedioxythiophene) : polystyrene sulfonate/Ag (ITO/ZnO/P3HT : PCBM : Pc/PEDOT : PSS/Ag). The donor-acceptor interfaces of devices with Pc were more stable than those without Pc in the active layer. During the thermal annealing process, the Pc in the P3HT : PCBM blends suppressed the crystallization of P3HT and PCBM, which was confirmed by optical microscopic images and UV-visible absorption spectra. The power conversion efficiency (PCE) of the device with Pc was reduced to no less than 70 % of its original efficiency after keeping it at 120 °C for 24 hours, while that of the non-Pc device was reduced to 13 % of its original efficiency after 24 hours at the same temperature. Based on these results, we propose a new Pc-blended organic solar cell that has advantages in the thermal annealing process.     

Effect of [6,6]‐phenyl‐C61‐butyric acid methyl ester on the morphology of poly(3‐hexylthiophene) film

The change of morphology of poly(3‐hexylthiophene) (P3HT) film as a result of blending with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) was studied using a freeze‐dry method. A porous structure was observed as the P3HT/PCBM solution was freeze‐dried. The pore size decreased as the proportion of PCBM increased in the P3HT/PCBM blended film. Additionally, the freeze‐dried P3HT/PCBM film was more resistant to the formation of PCBM crystals than that prepared by a spin‐coating method during the thermal annealing process. Homogeneous distribution of PCBM in the freeze‐dried P3HT/PCBM film was the main reason for the reduction of large PCBM crystal formation. Copyright © 2011 Society of Chemical Industry     

Solvent vapor‐induced self assembly and its influence on optoelectronic conversion of poly(3‐hexylthiophene): Methanofullerene bulk heterojunction photovoltaic cells

Nanoscale‐phase separation of electron donor/acceptor blends is crucial for efficient charge generation and collection in polymer bulk heterojunction photovoltaic cells. We investigated solvent vapor annealing effect of poly(3‐hexylthiophene) (P3HT)/methanofullerene (PCBM) blend on its morphology and optoelectronic properties. The organic solvents of choice for the treatment have a major effect on the morphology of P3HT/PCBM blend and the device performance. Ultraviolet‐visible absorption spectroscopy shows that specific solvent vapor annealing can induce P3HT self‐assembling to form well‐ordered structure; and hence, the absorption in the red region and the hole transport are enhanced. The solvent that has a poor solubility to PCBM would cause large PCBM clusters and result in a rough blend film. By combining an appropriate solvent vapor treatment and post‐thermal annealing of the devices, the power conversion efficiency is enhanced. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

溶剂对刮涂法制备P3HT:PCBM活性层薄膜形貌及光电性能的影响

选用2种混合溶剂氯仿+四氢化萘和二氯苯+氯仿配制活性液,通过刮涂法制备了P3HT∶PCBM活性层,研究了不同溶剂物化参数对P3HT∶PCBM活性层薄膜形貌及其组装电池光电性能的影响。应用显微图像分析仪、紫外可见分光光度计和台阶仪对P3HT∶PCBM活性层薄膜形貌进行了表征;采用X-射线衍射仪和紫外可见分光光度计分别测试了P3HT∶PCBM活性层的晶型结构和吸收光谱;在AM 1.5G、100mW/cm2光照下,测试了电池的光电性能。结果表明:采用二氯苯+氯仿(9∶1)混合溶剂较氯仿+四氢化萘(19∶1)混合溶剂制备的薄膜具有良好的均一性、平滑度、晶体结构,长吸收波长,用其组装的大面积(4cm2)柔性有机太阳能电池光电转换效率提高37%。     

Effect of solvent annealing on the crystallinity of spray coated ternary blend films prepared using low boiling point solvents

The effects of different post treatments on the spray coated P3HT:PPV:PCBM for an active layer in polymer solar cell were investigated using atomic force microscopy (AFM), UV–vis spectroscopy, photoluminescence (PL) spectroscopy and X-ray diffractometer (XRD). The annealing temperatures were varied from 130 °C to 150 °C and the annealing time was kept constant for 10 min. The RMS roughness of the sample that dried in the ambient condition was lower compared to other samples. This explained that the samples that undergo solvent and thermal annealing treatment had higher crystallinity of P3HT or phase separation in these samples is mostly favored. The peak absorption for P3HT:PPV:PCBM thin film is higher compared to P3HT:PCBM thin film. The better defined shoulders can be observed in the samples with solvent annealing treatment. The XRD spectra showed that the structure of the samples will evolve with high thermal annealing temperature (150 °C) due to a weak intermolecular force in P3HT molecules. This will contribute to the low crystallinity of the films which consequently affects the absorption properties of the films.     

Morphology,structure, and photovoltaic properties of poly(3‐hexylthiophene) and [6,6]‐phenyl‐C61‐butyric acid methyl ester‐based ternary blends doping with polystyrene of different tacticities

The influence of the polystyrene of different tacticities on the morphology, phase structure, and photovoltaic properties of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) blend has been extensively investigated. The atactic polystyrene (aPS) immiscible with P3HT tended to form the phase‐separated and columnar structure at low aPS weight ratio. Besides, the aPS could migrate to the surface of the films with PCBM phase distributing in the interfaces between P3HT and aPS domains at high aPS weight ratio of 75 wt %. The syndiotactic polystyrene (sPS) immiscible with P3HT could induce the crystallization of P3HT at low weight ratio of 3 wt %. The device based on aPS/P3HT/PCBM ternary blend showed of power conversion efficiency (PCE) of 1.2% even at aPS weight ratio of 50 wt %. However, the device based on sPS/P3HT/PCBM exhibited a sharp decrease in PCE value from 2.3% to 0.6% at sPS weight ratio of 3 wt %, due to the change in film morphology. The performance of the solar cell is believed to be determined by the morphology and phase structure of the ternary blends as revealed by the atomic force microscopy and UV‐vis spectra analysis. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41823.     

Synthesis and characterization of novel fulleropyrrolidine in P3HT blended bulk heterojunction solar cells

Synthesis of novel fullerene derived electron acceptors and characterization of their organic photovoltaic (OPV) properties is important for advancing fundamental knowledge towards developing next generation organic solar cells. We report the synthesis of a novel fulleropyrrolidine derivative C60-fused N-(3-methoxypropyl)-2-(carboxyethyl)-5-(4-cyanophenyl)fulleropyrrolidine (NCPF) by 1,3-dipolar cycloaddition reaction and characterization of NCPF by ¹H NMR, ¹³C NMR, MALDI-TOFMS, FT-IR, UV–Vis and CV. The synthesized NCPF fullerene derivative showed good solubility in common organic solvents such as chlorobenzene and 1,2 dichlorobenzene important for film formation, with optical absorbance and electronic properties comparable to PCBM. Optical micrographs of P3HT:PCBM thin films reveal formation of sparse, phase segregated needle shape PCBM micro-crystalline aggregates after 1 h of annealing at 150 °C whose length follows nucleation and growth kinetics over 24 h. In contrast, the P3HT:NCPF thin films exhibit homogeneity over 24 h, possibly due to weaker interparticle vanderWaals forces and/or stronger interactions with P3HT. This long term morphological stability of P3HT:NCPF is important for extended use in OPV applications. At an order of magnitude smaller scale, AFM of as cast and 10 min annealed at 150 °C P3HT:PCBM and P3HT:NCPF films reveal mostly smooth surfaces, with some NCPF cluster formation. Grazing incidence wide angle X-ray scattering (GIWAXS) measurements of P3HT:NCPF films indicate an increase of P3HT crystallinity with thermal annealing, leading to improvement in device performance. Photovoltaic devices fabricated with the active layer of P3HT:NCPF and P3HT:PCBM sandwiched between ITO/PEDOT:PSS and Al layer showed comparable performance upon short term annealing.     

Ternary Solvent System to Control the Morphology of Active Blend in Inverted Organic Solar Cells

Bulk heterojunction blend of poly(3-hexylthiophene)–[6,6]-phenyl-C₆₁-butyric acid methyl ester prepared using the ternary solvent mixture was used as the active layer of an inverted organic solar cell. The ternary solvent mixture consisted of a good solvent such as ortho-dichlorobenzene and two marginal solvents such as cyclohexanone and toluene offering limited solubility to the poly(3-hexylthiophene) component. Power conversion efficiency of inverted device was found to decrease from 2.74?±?0.05% in the unmodified device to 2.64?±?0.07% in the modified device. UV–visible measurement revealed less efficient photoabsorption in the mixed cosolvent-casted active layer due to insufficient and disordered crystallization of poly(3-hexylthiophene) domains.     

A new method to disperse CdS quantum dot-sensitized TiO2 nanotube arrays into P3HT:PCBM layer for the improvement of efficiency of inverted polymer solar cells

We report that the efficiency of ITO/nc-TiO₂/P3HT:PCBM/MoO₃/Ag inverted polymer solar cells (PSCs) can be improved by dispersing CdS quantum dot (QD)-sensitized TiO₂ nanotube arrays (TNTs) in poly (3-hexylthiophene) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) layer. The CdS QDs are deposited on the TNTs by a chemical bath deposition method. The experimental results show that the CdS QD-sensitized TNTs (CdS/TNTs) do not only increase the light absorption of the P3HT:PCBM layer but also reduce the charge recombination in the P3HT:PCBM layer. The dependence of device performances on cycles of CdS deposition on the TNTs was investigated. A high power conversion efficiency (PCE) of 3.52% was achieved for the inverted PSCs with 20 cyclic depositions of CdS on TNTs, which showed a 34% increase compared to the ITO/nc-TiO₂/P3HT:PCBM/MoO₃/Ag device without the CdS/TNTs. The improved efficiency is attributed to the improved light absorbance and the reduced charge recombination in the active layer.     

Improvement of the photovoltaic properties for P3HT:PCBM system annealed at the temperature in liquid crystalline regions induced by liquid crystal molecules

The poly(3-hexylthiophene):[6, 6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) bulk heterojunction organic photovoltaics (BHJ OPVs) showed a maximum value of 3.5 % by incorporating of 6 wt% nematic liquid crystals (NLCs) of 4-octyloxy-4′-cyanobiphenyls (8OCB) after annealing at the temperature of 70 °C in liquid crystalline transitions. The 8OCB was immiscible with P3HT, and the melting temperature of P3HT was not influenced at 8OCB doping amount below 10 wt%. Based on the UV–vis analysis, the conjugation length and chain order of P3HT should be the highest at 8OCB content of 6 wt% after annealing at 70 °C. The reflection peak of P3HT shifted to lower positions as the annealing temperature increasing from 70 to 130 °C, indicating that PCBM and 8OCB molecules could be incorporated into the lamellar spacing of P3HT crystallites at high annealing temperatures. The improvement of the solar cell device after annealing at 70 °C is probably due to the optimized phase separation morphology and relatively higher hole mobility in P3HT:PCBM:8OCB system. The 8OCB molecules in the liquid crystalline state are supposed to be a good template for the crystallization of P3HT, as well as the phase separation between P3HT and PCBM.     

Investigating the reduction in the absorption intensity of P3HT in polymer/fullerene “bilayers” coated using orthogonal solvents

We investigated the reduction in the absorption intensity of poly(3‐hexylthiophene) (P3HT) in a poly(3‐hexylthiophene)/(6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (P3HT/PCBM) “bilayer” heterojunction film that was fabricated using orthogonal solvents. The results show that even though P3HT is insoluble in dichloromethane (DCM), DCM could decrease the chain packing and the crystallinity of the P3HT film by the swelling effect. DCM also assists in the penetration of the PCBM into the P3HT underlayer during spin‐coating. After the DCM evaporates, the PCBM in the P3HT matrix hinders the self‐reorganization of P3HT, causing a drop in the absorption intensity of P3HT. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41757.     

A comparative study on the influence of alkyl thiols on the structural transformations in P3HT/PCBM and P3OT/PCBM blends

Herein, we present a comparative study on the structural transformations in P3HT/PCBM and P3OT/PCBM blends using octane (C₈) and dodecane (C₁₂) thiols as solvent additives. Addition of dodecane thiol to the blends promotes needle-like PCBM crystal formation. These crystals are found abundant in P3OT/PCBM and less in P3HT/PCBM blend and are identified by SAXS, DSC and SEM measurements. Using polymer of two different tail lengths, the SAXS results provide the first experimental support on the recent findings on fullerene intercalation around the crystalline boundaries in a semi-crystalline polymer. The UV–Visible measurements reveal that the absorption maximum show an appreciable red-shift and photoluminescence spectra infers that the donor/acceptor interface is mostly retained, upon dodecane thiol addition. These needle-like PCBM crystals obtained by annealing free approach in the blends and their dependence on the alkyl tail length of the polymer, would pave way for more effective design of organic photovoltaic devices.     

Self‐assembly of poly(3‐hexyl thiophene)‐b‐poly(ethylene oxide) into cylindrical micelles in binary solvent mixtures

Asymmetric block copolymer based on regioregular poly(3‐hexyl thiophene) (P3HT) and poly(ethylene oxide) (PEO) was synthesized through Heck reactions. The addition of PEO block has no influence in the effective conjugation length of P3HT block and apparently provides colloidal stability for the formation of stable nanostructures. Introduction of poor solvent to good solvent containing P3HT‐b‐PEO will induce the crystallization‐driven assembly of the P3HT into cylindrical micelles with a P3HT core, owing to π–π stacking of the conjugated backbone of P3HT. The absorption spectra of the cylindrical micelles reveal a red shift as compared to the polymer in good solvent, indicating the extension of conjugation length with an improved π–π stacking of the polymer chains within the cylindrical micelles. Our results indicated that cylindrical micelles with varied diameter and length can be obtained when solvent properties were varied using several different binary solvent mixtures. More interestingly, we demonstrate that ultrasonic processing can fragment the cylindrical micelles only when the ratio of poor solvent increases. This provides a facile and effective way to fabricate cylindrical micelles for applications in the area of polymer solar cell as well as organic optoelectronics device. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41186.     

Using water‐soluble nickel acetate as hole collection layer for stable polymer solar cells

We report polymer solar cells (PSCs) based on poly(3‐hexylthiophene (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) using water‐soluble nickel acetate (Ni(CH₃COO)₂, NiAc) instead of acidic poly(3,4‐ethylenedioxythiophene) : poly(styrenesulfonate) (PEDOT : PSS) as hole collection layer (HCL) between the indium tin oxide (ITO) electrode and photoactive layer. The NiAc layer can effectively decrease R_s and increase R_p and shows effective hole collection property. Under the illumination of AM1.5G, 100 mW/cm², the short‐circuit current density (J_sc) of the NiAc based device (ITO/NiAc/P3HT : PCBM/Ca/Al) reach 11.36 mA/cm², which is increased by 11% in comparison with that (10.19 mA/cm²) of PEDOT : PSS based device (ITO/PEDOT : PSS/P3HT : PCBM/Ca/Al). The power conversion efficiency of the NiAc based devices reach 3.76%, which is comparable to that (3.77%) of the device with PEDOT : PSS HCL under the same experimental conditions. Moreover, NiAc based PSCs show superior long‐term stability than PEDOT : PSS based PSCs. Our work gives a new option for HCL selection in designing more stable PSCs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Butterfly nanostructures via regioregularly grafted multi‐walled carbon nanotubes and poly(3‐hexylthiophene) to improve photovoltaic characteristics

Butterfly nanostructures were designed using multi‐walled carbon nanotubes (CNTs) grafted with regioregular poly(3‐hexylthiophene) (RR‐P3HT) chains (CNT‐graft‐P3HT). The secondary crystallization of RR‐P3HT free chains onto CNT‐graft‐P3HT reflected the donor–acceptor supramolecules with a butterfly configuration, in which the CNT acted as the body of the butterfly and seeded crystallization of P3HT free chains resulted in the wings having a width of 37–38 nm. Butterfly supramolecules demonstrated high melting point (241.2 °C), fusion enthalpy (31.5 J g^?1) and crystallinity (85.13%). High photoluminescence quenching and thus donating–accepting property were also detected for the butterfly nanohybrids with a bandgap energy of 1.94 eV. Incorporation of butterfly nanostructures in the active layer of photovoltaic devices (P3HT:butterfly) conspicuously affected the system characteristics including short circuit current density (J_sc; 10.84 mA cm^?2), fill factor (FF; 56%) and power conversion efficiency (PCE; 3.94%). The inclusion of phenyl‐C71‐butyric acid methyl ester molecules as second acceptor in thin‐film active layers further increased the efficacy of systems, i.e. J_sc of 12.23 mA cm^?2, FF of 63%, open circuit voltage of 0.66 V and PCE of 5.08%, without considering external treatments and additives. © 2018 Society of Chemical Industry     

Nonisothermal crystallization behaviors of poly(3‐hexylthiophene)/reduced graphene oxide nanocomposites

Poly(3‐hexylthiophene) (P3HT)/reduced graphene oxide (rGO) nanocomposites were prepared through in situ reduction of graphene oxide in the presence of P3HT. The nonisothermal crystallization behaviors of P3HT and P3HT/rGO nanocomposites were investigated by differential scanning calorimetry. The Avrami, Ozawa, and Mo models were used to analyze the nonisothermal kinetics. The addition of rGO remarkably increased the crystallization peak temperature and crystallinity of P3HT, but the crystallization half‐time revealed little variation. The crystallization activation energies were calculated by the Kissinger equation. The results suggested that rGO plays a twofold role in the nonisothermal crystallization of P3HT, that is, rGO promotes the crystallization of P3HT as nucleating agent, and meanwhile, it also restricts the motion of P3HT chains. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013