RESUMEN

Two wide-bandgap (WBG) conjugated polymers (PBPD-p and PBPD-m) based on phenyl-substituted benzodithiophene (BDT) with the different substitution position of the alkyl side chain and benzodithiophene-4,8-dione (BDD) units are designed and synthesized to investigate the influence of alkyl substitution position on the photovoltaic performance of polymers in polymer solar cells (PSCs). The thermogravimetric analysis, absorption spectroscopy, molecular energy level, X-ray diffraction, charge transport and photovoltaic performance of the polymers are systematically studied. Compared with PBPD-p, PBPD-m exhibits a slight blue-shift but a deeper highest occupied molecular orbital (HOMO) energy level, a tighter alkyl chain packing and a higher hole mobility. The PBPD-m-based PSCs blended with acceptor IT-4F shows a higher power conversion efficiency (PCE) of 11.95% with a high open-circuit voltage (Voc ) of 0.88 V, a short-circuit current density (Jsc ) of 19.76 mA cm-2 and a fill factor (FF) of 68.7% when compared with the PCE of 6.97% with a Voc of 0.81 V, a Jsc of 15.97 mA cm-2 and an FF of 53.9% for PBPD-p. These results suggest that it is a feasible and effective strategy to optimize photovoltaic properties of WBG polymers by changing the substitution position of alkyl side chain in PSCs.

Asunto(s)

RESUMEN

A novel molecular acceptor of TrBTIC (2,7,12-tris((2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile-7-benzothiadiazole-2-)truxene) is designed by attaching the 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile-benzothiadiazole (BTIC) electron-deficient unit to an electron-rich truxene core. TrBTIC has excellent solubility in common solvents and features good energy level matching with poly(3-hexylthiophene) (P3HT). Interestingly, P3HT can be readily dissolved in warm 1,2,4-trimethylbenzene (TMB), a green solvent, but crystallizes slowly with long-term aging in TMB at room temperature. A prephase separation can thus occur before active blend film deposition, and the separation degree can be easily controlled by varying the aging time. After 40 min of aging, the resulting active blend has the most appropriate phase separation with uniform nanowires, which forms favorable interpenetrating networks for exciton dissociation and charge transport. As a result, the device performance is improved from 6.62% to 8.25%. Excitingly, 8.25% is a new record for P3HT-based solar cells. The study not only provides an efficient nonfullerene acceptor for matching P3HT donors but also develops a promising processing technology to realize high-performance P3HT-based polymer solar cells with an efficiency over 8%.

RESUMEN

A new strategy of platinum(II) complexation is developed to regulate the crystallinity and molecular packing of polynitrogen heterocyclic polymers, optimize the morphology of the active blends, and improve the efficiency of the resulting nonfullerene polymer solar cells (NF-PSCs). The newly designed s-tetrazine (s-TZ)-containing copolymer of PSFTZ (4,8-bis(5-((2-butyloctyl)thio)-4-fluorothiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-alt-3,6-bis(4-octylthiophen-2-yl)-1,2,4,5-tetrazine) has a strong aggregation property, which results in serious phase separation and large domains when blending with Y6 ((2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile)), and produces a power-conversion efficiency (PCE) of 13.03%. By adding small amount of Pt(Ph)2 (DMSO)2 (Ph, phenyl and DMSO, dimethyl sulfoxide), platinum(II) complexation would occur between Pt(Ph)2 (DMSO)2 and PSFTZ. The bulky benzene ring on the platinum(II) complex increases the steric hindrance along the polymer main chain, inhibits the polymer aggregation strength, regulates the phase separation, optimizes the morphology, and thus improves the efficiency to 16.35% in the resulting devices. 16.35% is the highest efficiency for single-junction PSCs reported so far.

RESUMEN

Fine-tuning of the nanoscale morphologies of the active layers in polymer solar cells (PSCs) through various techniques plays a vital role in improving the photovoltaic performance. However, for emerging nonfullerene (NF) PSCs, the morphology optimization of the active-layer films empirically follows the methods originally developed in fullerene-based blends and lacks systematic studies. In this work, two solid additives with different volatilities, SA-4 and SA-7, are applied to investigate their influence on the morphologies and photovoltaic performances of NF-PSCs. Although both solid additives effectively promote the molecular packing of the NF acceptors, due to the higher volatility of SA-4, the devices processed with SA-4 exhibit a power conversion efficiency of 13.5%, higher than that of the control devices, and the devices processed with SA-7 exhibit poor performances. Through a series of detailed morphological analyses, it is found that the volatilization of SA-4 after thermal annealing is beneficial for the self-assembly packing of acceptors, while the residuals due to the incomplete volatilization of SA-7 have a negative effect on the film morphology. The results delineate the feasibility of applying volatilizable solid additives and provide deeper insights into the working mechanism, establishing guidelines for further material design of solid additives.

RESUMEN

Highly efficient nonfullerene polymer solar cells (PSCs) are developed based on two new phthalimide-based polymers phthalimide-difluorobenzothiadiazole (PhI-ffBT) and fluorinated phthalimide-ffBT (ffPhI-ffBT). Compared to all high-performance polymers reported, which are exclusively based on benzo[1,2-b:4,5-b']dithiophene (BDT), both PhI-ffBT and ffPhI-ffBT are BDT-free and feature a D-A1-D-A2 type backbone. Incorporating a second acceptor unit difluorobenzothiadiazole leads to polymers with low-lying highest occupied molecular orbital levels (≈-5.6 eV) and a complementary absorption with the narrow bandgap nonfullerene acceptor IT-4F. Moreover, these BDT-free polymers show substantially higher hole mobilities than BDT-based polymers, which are beneficial to charge transport and extraction in solar cells. The PSCs containing difluorinated phthalimide-based polymer ffPhI-ffBT achieve a substantial PCE of 12.74% and a large V oc of 0.94 V, and the PSCs containing phthalimide-based polymer PhI-ffBT show a further increased PCE of 13.31% with a higher J sc of 19.41 mA cm-2 and a larger fill factor of 0.76. The 13.31% PCE is the highest value except the widely studied BDT-based polymers and is also the highest among all benzothiadiazole-based polymers. The results demonstrate that phthalimides are excellent building blocks for enabling donor polymers with the state-of-the-art performance in nonfullerene PSCs and the BDT is not necessary for constructing such donor polymers.

RESUMEN

A novel wide-bandgap copolymer of PBDT-ODZ based on benzo[1,2-b:4,5-b' ]dithiophene (BDT) and 1,3,4-oxadiazole (ODZ) blocks is developed for efficient nonfullerene polymer solar cells (NF-PSCs). PBDT-ODZ exhibits a wide bandgap of 2.12 eV and a low-lying highest occupied molecular orbital (HOMO) level of -5.68 eV, which could match well with the low-bandgap acceptor of 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(4-hexylthienyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene (ITIC-Th), inducing a good complementary absorption from 300 to 800 nm and a minimal HOMO level offset (0.1 eV). The PBDT-ODZ:ITIC-Th devices exhibit a large open-circuit voltage (Voc ) of 1.08 eV and a low energy loss (Eloss ) of 0.50 eV, delivering a high power conversion efficiency (PCE) of 10.12%. By adding a small amount of copper(I) iodide (CuI) as an additive to form coordination complexes in the active blends, much higher device performances are achieved due to the improved absorption and crystallinity. After incorporating 4% of CuI, the PCE is elevated to 12.34%, with a Voc of 1.06 V, a Jsc of 17.1 mA cm-2 and a fill factor of 68.1%. This work not only provides a novel oxadiazole-containing wide-bandgap polymeric donor candidate for high-performance NF-PSCs but also presents an efficient morphology-optimization approach to elevate the PCE of NF-PSCs for future practical applications.

RESUMEN

Nonfullerene polymer solar cells (PSCs) have earned widespread and intense interest on account of their properties such as tunable energy levels, potential for low-cost production processes, reduced energy losses, and strong light absorption coefficients. Here, a water-/alcohol-soluble zwitterion perylene diimide zwitterion (PDI-z) consisted of sulfobetaine ion as a terminal substituent and PDI as a conjugated core was synthesized. PDI-z was employed as an electron-transport layer (ETL) for nonfullerene PSC devices, obtaining an optimal power conversion efficiency (PCE) above 11.23%. Moreover, nonfullerene PSCs with the PDI-z cathode interlayer displayed an excellent performance on a large scale of interlayer thickness, which was compatible with printing fabrication techniques. Additionally, the PDI-z interlayer presented good ability of modifying high work function metals (for instance, Au, Cu, and Ag) in nonfullerene devices, and the Ag device displayed a PCE of 9.38%. This work provides a good alternative ETL for high-efficiency nonfullerene PSCs.

RESUMEN

In recent years, rapid advances are achieved in polymer solar cells (PSCs) using nonfullerene small molecular acceptors. However, no research disclosing the influence of molecular weight (Mn ) of conjugated polymer on the nonfullerene device performance is reported. In this work, a series of polymers with different Mn s are synthesized to systematically investigate the connection between Mn and performance of nonfullerene devices for the first time. It is found that the device performance improves substantially as the Mn increases from 12 to 38 kDa and a power conversion efficiency (PCE) as high as 10.5% is realized. It has to be noted this PCE is achieved without using any additives and post-treatments, which is among the top efficiencies of additive- and post-treatment-free PSCs. Most importantly, the variation trend of the optimal active layer thickness and morphology is significantly different from the device with fullerene as acceptor. The findings clarify the effect of Mn on the performance of nonfullerene PSCs, which would benefit further efficiency improvement of nonfullerene PSCs.

RESUMEN

In this work, a nonfullerene polymer solar cell (PSC) based on a wide bandgap polymer donor PM6 containing fluorinated thienyl benzodithiophene (BDT-2F) unit and a narrow bandgap small molecule acceptor 2,2'-((2Z,2'Z)-((4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (IDIC) is developed. In addition to matched energy levels and complementary absorption spectrum with IDIC, PM6 possesses high crystallinity and strong π-π stacking alignment, which are favorable to charge carrier transport and hence suppress recombination in devices. As a result, the PM6:IDIC-based PSCs without extra treatments show an outstanding power conversion efficiency (PCE) of 11.9%, which is the record value for the as-cast PSC devices reported in the literature to date. Moreover, the device performances are insensitive to the active layer thickness (≈95-255 nm) and device area (0.20-0.81 cm2 ) with PCEs of over 11%. Besides, the PM6:IDIC-based flexible PSCs with a large device area of 1.25 cm2 exhibit a high PCE of 6.54%. These results indicate that the PM6:IDIC blend is a promising candidate for future roll-to-roll mass manufacturing and practical application of highly efficient PSCs.

RESUMEN

A new small molecule acceptor, m-ITIC-OR, based on indacenodithieno[3,2-b]thiophene core with meta-alkoxyphenyl side chains, is designed and synthesized. The m-ITIC-OR film shows broader and redshift absorption compared to its solution and matched energy levels with a hexafluoroquinoxaline-based polymer donor-HFQx-T. Here, polymer solar cells (PSCs) by blending an HFQx-T donor and an m-ITIC-OR acceptor as an active layer deliver the power conversion efficiency (PCE) of 6.36% without any posttreatment. The investigations demonstrate that the HFQx-T:m-ITIC-OR blend films possess higher and more balanced charge mobility, negligible bimolecular recombination, and nanoscale interpenetrating morphology after thermal annealing (TA) treatment. Through a simple TA treatment at 150 °C for 5 min, an impressive PCE of 9.3% is obtained. This efficiency is among one of the highest PCEs for additive free PSCs. This is the first time alkoxyphenyl side chain is introduced into nonfullerene electron acceptor; more interestingly, the new electron acceptor (m-ITIC-OR) in this work shows a great potential for highly efficient photovoltaic properties.

RESUMEN

For bulk heterojunction polymer solar cells (PSCs), the donors and acceptors featuring specific phase separation and concentration distribution within the electron donor/acceptor blends crucially affect the exciton dissociation and charge transportation. Herein, efficient and stable nonfullerene inverted PSCs incorporating a phase separated photoactive layer and a titanium chelate electrode modification layer are demonstrated. Water contact angle (WCA), scanning kelvin probe microscopy (SKPM), and atomic force microscopy (AFM) techniques are implemented to characterize the morphology of photoactive layers. Compared with the control conventional device, the short-circuit current density (Jsc) is enhanced from 14.74 to 17.45 mAcm-2. The power conversion efficiency (PCE) for the inverted PSCs with a titanium (diisopropoxide)-bis-(2,4-pentanedionate) (TIPD) layer increases from 9.67% to 11.69% benefiting from the declined exciton recombination and fairly enhanced charge transportation. Furthermore, the nonencapsulated inverted device with a TIPD layer demonstrates the best long-term stability, 85% of initial PCE remaining and an almost undecayed open-circuit voltage (Voc) after 1440 h. Our results reveal that the titanium chelate is an excellent electrode modification layer to incorporate with a vertical phase separated photoactive layer for producing high-efficiency and high-stability inverted nonfullerene PSCs.

RESUMEN

Rapid improvements in nonfullerene polymer solar cells (PSCs) have brought power conversion efficiencies to greater than 12%. To further improve device performance, a fundamental understanding of the correlations between structure and performance is essential. In this paper, based on a typical high-performance system consisting of J61(one donor-acceptor (D-A) copolymer of benzodithiophene and fluorine substituted benzotriazole) and ITIC (3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene), a 3D structural model is directly imaged by employing high-resolution atomic force microscopy (AFM). Hierarchical morphologies ranging from fiberlike crystallites, several nanometers in size, to a bicontinuous morphology, having domains tens of nanometers in size, are observed. A fibrillar interpenetrating networks of J61-rich domains embedded in a matrix comprised of a J61/ITIC is seen, reflecting the partial miscibility of J61 with ITIC. These hierarchical nanostructural characteristics are coupled to significantly enhanced exciton dissociation, and further contribute to photocurrent and final device performance.

RESUMEN

High-performance nonfullerene polymer solar cells (PSCs) are developed by integrating the nonfullerene electron-accepting material 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophne) (ITIC) with a wide-bandgap electron-donating polymer PTzBI or PTzBI-DT, which consists of an imide functionalized benzotriazole (TzBI) building block. Detailed investigations reveal that the extension of conjugation can affect the optical and electronic properties, molecular aggregation properties, charge separation in the bulk-heterojunction films, and thus the overall photovoltaic performances. Single-junction PSCs based on PTzBI:ITIC and PTzBI-DT:ITIC exhibit remarkable power conversion efficiencies (PCEs) of 10.24% and 9.43%, respectively. To our knowledge, these PCEs are the highest efficiency values obtained based on electron-donating conjugated polymers consisting of imide-functionalized electron-withdrawing building blocks. Of particular interest is that the resulting device based on PTzBI exhibits remarkable PCE of 7% with the thickness of active layer of 300 nm, which is among the highest values of nonfullerene PSCs utilizing thick photoactive layer. Additionally, the device based on PTzBI:ITIC exhibits prominent stability, for which the PCE remains as 9.34% after thermal annealing at 130 °C for 120 min. These findings demonstrate the great promise of using this series of wide-bandgap conjugated polymers as electron-donating materials for high-performance nonfullerene solar cells toward high-throughput roll-to-roll processing technology.

RESUMEN

A nonfullerene polymer solar cell with a high efficiency of 9.26% is realized by using benzodithiophene-alt-fluorobenzotriazole copolymer J51 as a medium-bandgap polymer donor and the low-bandgap organic semiconductor ITIC with high extinction coefficients as the acceptor.