Beibei Qiu

Fine‐Tuning of Molecular Packing and Energy Level through Methyl Substitution Enabling Excellent Small Molecule Acceptors for Nonfullerene Polymer Solar Cells with Efficiency up to 12.54%

A novel small molecule acceptor MeIC with a methylated end-capping group is developed. Compared to unmethylated counterparts (ITCPTC), MeIC exhibits a higher lowest unoccupied molecular orbital (LUMO) level value, tighter molecular packing, better crystallites quality, and stronger absorption in the range of 520-740 nm. The MeIC-based polymer solar cells (PSCs) with J71 as donor, achieve high power conversion efficiency (PCE), up to 12.54% with a short-circuit current (JSC ) of 18.41 mA cm-2 , significantly higher than that of the device based on J71:ITCPTC (11.63% with a JSC of 17.52 mA cm-2 ). The higher JSC of the PSC based on J71:MeIC can be attributed to more balanced μh /μe , higher charge dissociation and charge collection efficiency, better molecular packing, and more proper phase separation features as indicated by grazing incident X-ray diffraction and resonant soft X-ray scattering results. It is worth mentioning that the as-cast PSCs based on MeIC also yield a high PCE of 11.26%, which is among the highest value for the as-cast nonfullerene PSCs so far. Such a small modification that leads to so significant an improvement of the photovoltaic performance is a quite exciting finding, shining a light on the molecular design of the nonfullerene acceptors.

Side Chain Engineering on Medium Bandgap Copolymers to Suppress Triplet Formation for High‐Efficiency Polymer Solar Cells

Suppression of carrier recombination is critically important in realizing high-efficiency polymer solar cells. Herein, it is demonstrated difluoro-substitution of thiophene conjugated side chain on donor polymer can suppress triplet formation for reducing carrier recombination. A new medium bandgap 2D-conjugated D-A copolymer J91 is designed and synthesized with bi(alkyl-difluorothienyl)-benzodithiophene as donor unit and fluorobenzotriazole as acceptor unit, for taking the advantages of the synergistic fluorination on the backbone and thiophene side chain. J91 demonstrates enhanced absorption, low-lying highest occupied molecular orbital energy level, and higher hole mobility, in comparison with its control polymer J52 without fluorination on the thiophene side chains. The transient absorption spectra indicate that J91 can suppress the triplet formation in its blend film with n-type organic semiconductor acceptor m-ITIC (3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(3-hexylphenyl)-dithieno[2,3-d:2,3-d]-s-indaceno[1,2-b:5,6-b]-dithiophene). With these favorable properties, a higher power conversion efficiency of 11.63% with high VOC of 0.984 V and high JSC of 18.03 mA cm-2 is obtained for the polymer solar cells based on J91/m-ITIC with thermal annealing. The improved photovoltaic performance by thermal annealing is explained from the morphology change upon thermal annealing as revealed by photoinduced force microscopy. The results indicate that side chain engineering can provide a new solution to suppress carrier recombination toward high efficiency, thus deserves further attention.

A low cost and high performance polymer donor material for polymer solar cells

The application of polymer solar cells requires the realization of high efficiency, high stability, and low cost devices. Here we demonstrate a low-cost polymer donor poly[(thiophene)-alt-(6,7-difluoro-2-(2-hexyldecyloxy)quinoxaline)] (PTQ10), which is synthesized with high overall yield of 87.4% via only two-step reactions from cheap raw materials. More importantly, an impressive efficiency of 12.70% is obtained for the devices with PTQ10 as donor, and the efficiency of the inverted structured PTQ10-based device also reaches 12.13% (certificated to be 12.0%). Furthermore, the as-cast devices also demonstrate a high efficiency of 10.41% and the devices exhibit insensitivity of active layer thickness from 100u2009nm to 300u2009nm, which is conductive to the large area fabrication of the devices. In considering the advantages of low costxa0and high efficiency with thickness insensitivity, we believe that PTQ10 will be a promising polymer donor for commercial application of polymer solar cells.A problem that hinders the commercialization of polymer solar cells is the complication in synthesis and thus the low yield and high cost of the polymers. Here, Sun et al. synthesize a new polymer via a two-step process with a yield close to 90% and show high photovoltaic performance with efficiency of 12%.

High performance as-cast semitransparent polymer solar cells

Semi-transparent polymer solar cells (ST-PSCs) have attracted great attention recently because of their potential for application in smart windows, etc. Here, we fabricated ST-PSCs based on a low band-gap conjugated polymer, PTB7-Th, as the donor and a narrow band-gap n-type organic semiconductor (n-OS), ITVfIC, as the acceptor. The active layer (with a thickness of 100 nm) of the ST-PSC exhibits a high average transmittance (AT) of 73.46% in the wavelength range of 400–600 nm. The as-cast ST-PSC with 15 nm Ag as the cathode without any additive or thermal-annealing treatment shows a higher power conversion efficiency (PCE) of 8.21% with an AT of 33.7%, which is one of the highest values for ST-PSCs without extra treatment. In addition, the ST-PSCs show good thermal stability with 91% of their original PCE value retained after high temperature treatment at 200 °C for 2 hours. The higher PCE and good stability indicate that the ST-PSC has potential for practical application and the narrow bandgap ITVfIC could be a promising n-OS acceptor for the fabrication of ST-PSCs.

High‐Efficiency All‐Small‐Molecule Organic Solar Cells Based on an Organic Molecule Donor with Alkylsilyl‐Thienyl Conjugated Side Chains

Two medium-bandgap p-type organic small molecules H21 and H22 with an alkylsily-thienyl conjugated side chain on benzo[1,2-b:4,5-b]dithiophene central units are synthesized and used as donors in all-small-molecule organic solar cells (SM-OSCs) with a narrow-bandgap n-type small molecule 2,2-((2Z,2Z)-((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) as the acceptor. In comparison to H21 with 3-ethyl rhodanine as the terminal group, H22 with cyanoacetic acid esters as the terminal group shows blueshifted absorption, higher charge-carrier mobility and better 3D charge pathway in blend films. The power conversion efficiency (PCE) of the SM-OSCs based on H22:IDIC reaches 10.29% with a higher open-circuit voltage of 0.942 V and a higher fill factor of 71.15%. The PCE of 10.29% is among the top efficiencies of nonfullerene SM-OSCs reported in the literature to date.

A universal nonfullerene electron acceptor matching with different band-gap polymer donors for high-performance polymer solar cells

Unlike fullerene derivatives, current nonfullerene n-type organic semiconductor (n-OS) electron acceptors can rarely work efficiently with different band-gap polymer donors in polymer solar cells (PSCs). To address this issue, we designed and synthesized a new n-OS electron acceptor, namely m-MeIC, which is proved to be effective with different band-gap polymer donors including wide band-gap J71, medium band-gap PBDB-T and low band-gap PCE-10. Photovoltaic devices based on J71:m-MeIC and PBDB-T:m-MeIC achieved power conversion efficiencies (PCEs) as high as 12.08% and 10.93%, respectively. The difference in PCEs between the devices based on J71 and PBDB-T is mainly ascribed to the gap of the open circuit voltage. It should be mentioned that the J71-based device exhibited an energy loss of 0.62xa0eV, which is significantly lower than the most reported energy loss. For the low band-gap polymer donor PCE-10, the device also showed a relatively high PCE of 8.34%. The different device performances are analyzed in depth from charge transport and collection, to recombination loss mechanism and morphology of blend films. This work reveals that the new n-type organic semiconductor is very promising as a universal nonfullerene acceptor, pairing with different band-gap polymer donors.

High-efficiency organic solar cells based on a small-molecule donor and a low-bandgap polymer acceptor with strong absorption

Solution-processed organic solar cells (OSCs) have been attracting more and more attention for a series of well-known advantages, and power conversion efficiencies (PCEs) of over 11% have been reported. However, the highest PCE of the OSCs based on small molecule donor/polymer acceptor blends is only 4.82%, which was much lower than those of other types of OSCs due to weak absorption of the polymer acceptor and the unbalanced charge carrier mobility of the small molecule donor and the polymer acceptor. Here, we fabricated small molecule donor/polymer acceptor-based OSCs using the wide bandgap SM1 and DR3TBDTT as the small molecular donor and the low-bandgap n-type conjugated polymer PZ1 as the polymer acceptor. With the treatment of a solvent additive, which can promote the absorption intensity, enhance the carrier mobility and suppress the charge carrier recombination, the SM1-based devices and the DR3TBDTT-based devices show PCEs of 3.97% and 5.86%, respectively. It is worth mentioning that the PCE of 5.86% is the state-of-the-art efficiency for OSCs based on the small molecular donor/polymer acceptor system.

Effects of Alkoxy and Fluorine Atom Substitution of Donor Molecules on the Morphology and Photovoltaic Performance of All Small Molecule Organic Solar Cells

Two benzothiadiazole (BT)-based small-molecule donors, SM-BT-2OR with alkoxy side chain and SM-BT-2F with fluorine atom substitution, were designed and synthesized for investigating the effect of the substituents on the photovoltaic performance of the donor molecules in all small molecule organic solar cells (SM-OSCs). Compared to SM-BT-2OR, the film of SM-BT-2F exhibited red-shifted absorption and deeper HOMO level of −5.36 eV. When blending with n-type organic semiconductor (n-OS) acceptor IDIC, the as-cast devices displayed similar PCE values of 2.33 and 2.76% for the SM-BT-2OR and SM-BT-2F-based devices, respectively. The SM-BT-2OR-based devices with thermal annealing (TA) at 120°C for 10 min showed optimized PCE of 7.20%, however, the SM-BT-2F-based device displayed lower PCE after the TA treatment, which should be ascribed to the undesirable morphology and molecular orientation. Our results reveal that for the SM-OSCs, the substituent groups of small molecule donors have great impact on the film morphology, as well as the photovoltaic performance.