Xia Guo

Replacing Alkoxy Groups with Alkylthienyl Groups: A Feasible Approach To Improve the Properties of Photovoltaic Polymers†

Polymer solar cells (PSCs) have attracted much attention because of their potential application in flexible, light-weight, and low-cost large-area devices through roll-to-roll printing. The bulk heterojunction PSCs showed advanced features in realizing high efficiencies and solution-processible devices. The active layer in this kind of device consists of an interpenetrating network formed by an electron-donor material blended with an electron-acceptor material. 3] Typically, conjugated polymers are used as electron donors and fullerene derivatives are used as the electron acceptors in the PSCs. Recently, power conversion efficiencies (PCEs) of 6–7% have been realized by using new conjugated polymer donors or new fullerene-derived acceptors. Short circuit current density (Jsc), open circuit voltage (Voc), and fill factors (FF) are key parameters for a PSC device, because the PCE of the device is proportional to the values of the three parameters. To broaden the response wavelength range of a PSC device by using conjugated side chains or narrowband-gap conjugated polymers is an effective way to realize high Jsc values. Conjugated polymers with lower HOMO levels are helpful in realizing high Voc and PCE values, as the Voc value of PSCs is directly proportional to the offset between the HOMO level of electron donor and the LUMO level of electron acceptor. PSiFDTBT, PFDTBT, and PCDTBT are three excellent examples for this concept. Consequently, by using conjugated polymers with lower HOMO levels and also narrow band gaps, high PCEs were realized in different families of conjugated polymers. Conjugated polymers based on benzo[1,2-b :4,5-b’]dithiophene (BDT) units have attracted interest as electron donors in the PSC field in recent years, since the report of Hou and Yang et al. on the synthesis and photovoltaic properties of a series of copolymers based on BDT. Many copolymers of BDT with different conjugated units, such as thieno[3,4b]thiophene (TT), 4,7-dithiophene-2-yl-2,1,3-benzothiadiazole (DTBT), N-alkylthieno[3,4-c]pyrrole-4,6-dione (TPD), and bithiazole, etc. were synthesized, and the copolymers showed promising photovoltaic properties. In these BDT-based polymers, the alternative copolymers of BDT and TT, namely PBDTTTs, are an important family of photovoltaic materials. For additional improvements in the photovoltaic performance of the PBDTTTs, structural modifications brought about by using different substituents on BDT, or the copolymerized moieties is of great importance. For example, Liang et al. introduced a fluorine atom into the TT unit of the PBDTTTs, and the HOMO level of the resulting polymer was successfully lowered by approximately 0.12 eV, and thus a higher Voc value was achieved, resulting in a great improvement of PCE. Hou et al. optimized PBDTTTs further by replacing the alkoxycarbonyl group on the TT unit with the alkylcarbonyl groups. The structural modification can also be carried out on the BDT units. In this work, we designed an 5-alkylthiophene-2-yl-substituted BDT monomer and synthesized two new PBDTTT-based polymers having either the thienylsubstituted BDT with alkoxycarbonyl-substituted thieno[3,4b]thiophene (TT-E) or the alkylcarbonyl-substituted thieno[3,4-b]thiophene (TT-C); that is PBDTTT-E-Tand PBDTTTC-T, respectively (Scheme 1). To fully investigate the effect of the thienyl-substituted BDTon the photovoltaic properties of the polymers, two corresponding PBDTTT polymers based on the alkoxy-substituted BDT (BDT-O), PBDTTT-E and PBDTTT-C (Scheme 1), were also prepared. The synthetic route of the thienyl-substituted BDT monomer (BDT-T) is shown in Scheme 1. The branched alkyl group 2-ethylhexyl was employed as the side chain on the thiophene to guarantee high solubility of the target polymers. The TT-E and TT-C monomers are commercially available. The polymers were prepared through a Stille coupling reaction between the bis(trimethyltin) BDT monomers (BDT-T and BDT-O) and the bromides (TT-E and TTC) as shown in Scheme 1. All the polymers are soluble in chloroform (CHCl3), chlorobenzene, and dichlorobenzene. Thermogravimetric analysis (TGA) measurements were employed to evaluate the thermal stability of the polymers. We found that the two-dimentional (2D) conjugated polymers based on alkylthienyl-substituted BDTs are much more stable than their analogues, the alkoxy-substituted BDTs. The TGA plots of these four polymers are shown in Figure 1. It can be seen that the decomposition temperatures [*] Dr. L. Huo, S. Zhang, F. Xu, Prof. J. Hou State Key Laboratory of Polymer Physics and Chemistry Beijing National Laboratory for Molecular Sciences Institute of Chemistry, Chinese Academy of Sciences Beijing 100190 (China) E-mail: hjhzlz@iccas.ac.cn

Dual Plasmonic Nanostructures for High Performance Inverted Organic Solar Cells

Polymer-fullerene-based bulk heterojunction (BHJ) solar cells have many advantages, including low-cost, low-temperature fabrication, semi-transparency, and mechanical fl exibility. [ 1 , 2 ] However, there is a mismatch between optical absorption length and charge transport scale. [ 3 , 4 ] These factors lead to recombination losses, higher series resistances, and lower fi ll factors. Attempts to optimize both the optical and electrical properties of the photoactive layer in organic solar cells (OSCs) inevitably result in a demand to develop a device architecture that can enable effi cient optical absorption in fi lms thinner than the optical absorption length. [ 5 , 6 ] Here, we report the use of two metallic nanostructures to achieve broad light absorption enhancement, increased shortcircuit current ( J sc ), and improved fi ll factor ( FF ) simultaneously based on the new small-bandgap polymer donor poly{[4,8-bis(2-ethyl-hexyl-thiophene-5-yl)-benzo[1,2-b:4,5-b ′ ]dithiophene2,6-diyl]alt -[2-(2 ′ -ethyl-hexanoyl)-thieno[3,4-b]thiophen-4,6-diyl]} (PBDTTT-C-T) in BHJ cells. [ 7 ] The dual metallic nanostructure consists of a metallic nanograting electrode as the back refl ector and metallic nanoparticles (NPs) embedded in the active layer. Consequently, we achieve the high power conversion effi ciency (PCE) of 8.79% for a single-junction BHJ OSC. Recently, plasmonic nanostructures have been introduced into solar cells for highly effi cient light harvesting. [ 5 , 8–17 ] Two types of plasmonic resonances, surface plasmonic resonances (SPRs) [ 18–22 ] and localized plasmonic resonances (LPRs), [ 11–14 ] can be used for enhancing light absorption. Metallic gratingbased light-trapping schemes have been investigated in traditional inorganic photovoltaic cells. [ 18–20 ] For metallic nanogratings, which can support SPRs, it is still challenging to experimentally demonstrate the enhancement of PCE in OSCs owing to the obvious issue of solution processing of

Improving the Ordering and Photovoltaic Properties by Extending π–Conjugated Area of Electron‐Donating Units in Polymers with D‐A Structure

A systematic molecular design process from PBDTTT-S to PBDTDTTT-S-T, a high-performance semiconducting polymer for organic photovoltaics, has been achieved by enhancing structural order, self-assembly and carrier mobility. Solar cells made from PBDTDTTT-S-T blended with PC(70) BM show a power conversion efficiency (PCE) of 7.81%, which is 25% higher than that of the parent PBDTTT-S.

Efficient Polymer Solar Cells Based on Benzothiadiazole and Alkylphenyl Substituted Benzodithiophene with a Power Conversion Efficiency over 8

A new copolymer PBDTP-DTBT based on benzothiadiazole and alkylphenyl substituted benzodithiophene is synthesized and characterized. The correlation of the evolution of the morphology and photovoltaic performance is investigated. The power conversion efficiency of the polymer solar cells based on PBDTP-DTBT/PC71 BM (1:1.5, w/w) reaches up to 8.07%, under the irradiation of AM 1.5G, 100 mW/cm(2) .

Synergistic Effect of Fluorination on Molecular Energy Level Modulation in Highly Efficient Photovoltaic Polymers

The synergistic effect of fluorination on molecular energy level modulation is realized by introducing fluorine atoms onto both the donor and the acceptor moieties in a D-A polymer, and as a result, the polymer solar cell device based on the trifluorinated polymer, PBT-3F, shows a high efficiency of 8.6%, under illumination of AM 1.5G, 100 mW cm(-) (2) .

From Binary to Ternary Solvent: Morphology Fine‐tuning of D/A Blends in PDPP3T‐based Polymer Solar Cells

For the PDPP3T/PCBM system investigated here, atomic force microscopy, resonant soft X-ray scattering, and grazing incidence wide angle X-ray scattering are used as an initial set of tools to determine the surface texture, the bulk compositional morphology, and the crystallization behavior, respectively. We find systematic variations and relate them to device performance. A solvent mixture of DCB/CF/DIO = 76:19:5 (v/v/v) yields a PCE of 6.71%.

High efficiency polymer solar cells based on poly(3-hexylthiophene)/indene-C70 bisadduct with solvent additive

The photovoltaic performance of the polymer solar cells (PSCs) based on poly(3-hexylthiophene) (P3HT) as donor and indene-C70 bisadduct (IC70BA) as acceptor was optimized by using 3 vol% high boiling point solvent additive of 1-chloronaphthalene (CN), N-methyl pyrrolidone (NMP), 1,8-octanedithiol (OT) or 1,8-diiodooctane (DIO) without solvent annealing. The optimized PSC based on P3HT : IC70BA (1 : 1, w/w) with 3 vol% CN and pre-thermal annealing at 150 °C for 10 min, exhibits a high power conversion efficiency (PCE) of 7.40% with Voc of 0.87 V, Jsc of 11.35 mA cm−2 and FF of 75.0%, under the illumination of AM1.5G, 100 mW cm−2. The PCE of 7.40%, the Voc of 0.87 V, and the FF of 75.0% are all the highest values reported in the literature so far for P3HT-based PSCs. The high efficiency is due to the optimized P3HT/IC70BA interpenetrating network and stronger absorption of the active layer by using the additive treatment. Taking into account the advantages of thickness-insensitivity and good reproducibility of the photovoltaic performance of the P3HT-based PSCs as well as the simple device fabrication processes without the need of solvent annealing, the high-efficiency PSCs based on P3HT : IC70BA using CN additive are very promising for future commercialization of PSC devices.

Enhanced Photovoltaic Performance by Modulating Surface Composition in Bulk Heterojunction Polymer Solar Cells Based on PBDTTT-C-T/PC71BM

For the blend film of PBDTTT-C-T:PC71 BM, the use of 1,8-diiodooctane as the solvent additive enriches the polymer at the top surface, so that a power conversion efficiency of 9.13% is recorded in the inverted polymer solar cell based on the blend, which is much higher than that of the device with conventional structure.

Influence of D/A Ratio on Photovoltaic Performance of a Highly Efficient Polymer Solar Cell System

A new copolymer PIDTDTQx based on indacenodithiophene and quinoxaline is synthesized and characterized. The correlation between the D/A ratio, mobility, and photovoltaic properties, as well as morphology of the D/A blend based on a PIDTDTQx:PC(70) BM system is investigated. The power conversion efficiency of the polymer solar cells based on PIDTDTQx/PC(70) BM (1:4, w/w) reaches 7.51%.

PDT‐S‐T: A New Polymer with Optimized Molecular Conformation for Controlled Aggregation and π–π Stacking and Its Application in Efficient Photovoltaic Devices

The correlation among molecular conformation, the crystallinity of the morphology, propensity for π-π stacking, J- versus H-aggregation, and photovoltaic performance have been studied based on two newly designed polymers, PBDTTT-S-T and PDT-S-T. The results show that more linear backbone structure is helpful to improve photovoltaic properties of the polymer, and therefore, molecular conformation should be considered for molecular design of photovoltaic polymers.