Indacenodithienothiophene (IDTT)-based postfullerene electron acceptors, such as ITIC (2,2'-[[6,6,12,12-tetrakis(4-hexylphenyl)-6,12-dihydrodithieno[2,3- d:2',3'- d']-s-indaceno[1,2- b:5,6- b']dithiophene-2,8-diyl]-bis[methylidyne(3-oxo-1 H-indene-2,1(3 H)-diylidene)]]bis[propanedinitrile]), have become synonymous with high power conversion efficiencies (PCEs) in bulk heterojunction (BHJ) polymer solar cells (PSCs). Here we systematically investigate the influence of end-group fluorination density and positioning on the physicochemical properties, single-crystal packing, end-group redistribution propensity, and BHJ photovoltaic performance of a series of ITIC variants, ITIC- nF ( n = 0, 2, 3, 4, and 6). Increasing n from 0 → 6 contracts the optical bandgap, but only marginally lowers the LUMO for n > 4. This yields enhanced photovoltaic short-circuit current density and good open-circuit voltage, so that ITIC-6F achieves the highest PCE of the series, approaching 12% in blends with the PBDB-TF donor polymer. Single-crystal diffraction reveals that the ITIC- nF molecules cofacially interleave with ITIC-6F having the shortest π-π distance of 3.28 A. This feature together with ZINDO-level computed intermolecular electronic coupling integrals as high as 57 meV, and B3LYP/DZP-level reorganization energies as low as 147 meV, rival or surpass the corresponding values for fullerenes, ITIC-0F, and ITIC-4F, and track a positive correlation between the ITIC- nF space-charge limited electron mobility and n. Finally, a heretofore unrecognized solution-phase redistribution process between the 2-(3-oxo-indan-1-ylidene)-malononitrile-derived end-groups (EGs) of IDTT-based NFAs, i.e., EG1-IDTT-EG1 + EG2-IDTT-EG2 ⇌ 2 EG1-IDTT-EG2, with implications for the entire ITIC PSC field, is identified and mechanistically characterized, and the effects on PSC performance are assessed.

Fluorination Effects on Indacenodithienothiophene Acceptor Packing and Electronic Structure, End-Group Redistribution, and Solar Cell Photovoltaic Response.

The majority of organic semiconductors have a low relative dielectric constant (er 6) has attracted a very limited attention. Moreover, high performance OSCs based on high dielectric constant photovoltaic materials are still in their infancy. Herein, we report an oligoethylene oxide side chain-containing non-fullerene acceptor (ITIC-OE) with a high relative dielectric constant of er ≈ 9.4, which is two times larger than that of its alkyl chain-containing counterpart ITIC. Encouragingly, the OSCs based on ITIC-OE show a high power conversion efficiency of 8.5%, which is the highest value for OSCs that employ high dielectric constant materials. Nevertheless, this value is lower than those of ITIC-based control devices. The less phase-separated morphology in blend films due to the reduced crystallinity of ITIC-OE and the too good miscibility between PBDB-T and ITIC-OE are responsible for the lower device performance. This work suggests additional prerequisites to make high dielectric constants play a significant role in OSCs.

A high dielectric constant non-fullerene acceptor for efficient bulk-heterojunction organic solar cells

Conjugated polymer chains have many degrees of conformational freedom and interact weakly with each other, resulting in complex microstructures in the solid state. Understanding charge transport in such systems, which have amorphous and ordered phases exhibiting varying degrees of order, has proved difficult owing to the contribution of electronic processes at various length scales. The growing technological appeal of these semiconductors makes such fundamental knowledge extremely important for materials and process design. We propose a unified model of how charge carriers travel in conjugated polymer films. We show that in high-molecular-weight semiconducting polymers the limiting charge transport step is trapping caused by lattice disorder, and that short-range intermolecular aggregation is sufficient for efficient long-range charge transport. This generalization explains the seemingly contradicting high performance of recently reported, poorly ordered polymers and suggests molecular design strategies to further improve the performance of future generations of organic electronic materials.

http://absimage.aps.org/image/MAR14/MWS_MAR14-2013-020288.pdf

A general relationship between disorder, aggregation and charge transport in conjugated polymers

Quasi-two-dimensional (quasi-2D) Ruddlesden–Popper (RP) perovskites such as BA2Csn–1PbnBr3n+1 (BA = butylammonium, n > 1) are promising emitters, but their electroluminescence performance is limited by a severe non-radiative recombination during the energy transfer process. Here, we make use of methanesulfonate (MeS) that can interact with the spacer BA cations via strong hydrogen bonding interaction to reconstruct the quasi-2D perovskite structure, which increases the energy acceptor-to-donor ratio and enhances the energy transfer in perovskite films, thus improving the light emission efficiency. MeS additives also lower the defect density in RP perovskites, which is due to the elimination of uncoordinated Pb2+ by the electron-rich Lewis base MeS and the weakened adsorbate blocking effect. As a result, green light-emitting diodes fabricated using these quasi-2D RP perovskite films reach current efficiency of 63 cd A−1 and 20.5% external quantum efficiency, which are the best reported performance for devices based on quasi-2D perovskites so far. Owing to large exciton binding energy, quasi-2D perovskite is promising for light-emitting application, yet inhomogeneous phases distribution limits the potential. Here, the authors improve the performance by using MeS additive to regulate the phase distribution and to reduce defect density in the films.

/pdf/smoothing-the-energy-transfer-pathway-in-quasi-2d-perovskite-i2nia41mip.pdf

Smoothing the energy transfer pathway in quasi-2D perovskite films using methanesulfonate leads to highly efficient light-emitting devices.

In organic solar cells, the charge-transfer (CT) electronic states that form at the interface between the electron-donor (D) and electron-acceptor (A) materials have a crucial role in exciton-dissociation, charge-separation and charge-recombination processes. Since the introduction of active layers consisting of D–A bulk heterojunctions, CT states have been the focus of extensive experimental and theoretical studies. In this Review, we assess the current understanding of CT states and describe how factors such as the geometry of the D–A interface, electronic polarization and the extent of electron delocalization affect their nature and influence the radiative and non-radiative decay processes. We focus on the description and application of fundamental concepts, which provides the framework to discuss the path to organic solar cells with efficiencies comparable to those in inorganic photovoltaic technologies. The charge-transfer electronic states that form at the interfaces between electron-donor and electron-acceptor components have a key role in the electronic processes in organic solar cells. This Review describes the current understanding of how these charge-transfer states affect device performance.

Charge-transfer electronic states in organic solar cells

Quasi-2D Ruddlesden-Popper halide perovskites with a large exciton binding energy, self-assembled quantum wells, and high quantum yield draw attention for optoelectronic device applications. Thin films of these quasi-2D perovskites consist of a mixture of domains having different dimensionality, allowing energy funneling from lower-dimensional nanosheets (high-bandgap domains) to 3D nanocrystals (low-bandgap domains). High-quality quasi-2D perovskite (PEA)2 (FA)3 Pb4 Br13 films are fabricated by solution engineering. Grazing-incidence wide-angle X-ray scattering measurements are conducted to study the crystal orientation, and transient absorption spectroscopy measurements are conducted to study the charge-carrier dynamics. These data show that highly oriented 2D crystal films have a faster energy transfer from the high-bandgap domains to the low-bandgap domains (<0.5 ps) compared to the randomly oriented films. High-performance light-emitting diodes can be realized with these highly oriented 2D films. Finally, amplified spontaneous emission with a low threshold 4.16 µJ cm-2 is achieved and distributed feedback lasers are also demonstrated. These results show that it is important to control the morphology of the quasi-2D films to achieve efficient energy transfer, which is a critical requirement for light-emitting devices.

Efficient Energy Funneling in Quasi-2D Perovskites: From Light Emission to Lasing

Ultraviolet-ozone surface modification for non-wetting hole transport materials based inverted planar perovskite solar cells with efficiency exceeding 18%

Impact of Nonfullerene Molecular Architecture on Charge Generation, Transport, and Morphology in PTB7-Th-Based Organic Solar Cells

It is commonly believed that large dielectric constants are required for efficient charge separation in polymer photovoltaic devices. However, many polymers used in high-performance solar cells do not possess high dielectric constants. In this work, the effect of polymer–fullerene interactions on the dielectric environment of the active layer blend and the device performance for several donor–acceptor conjugated polymer systems is investigated. It is found that, while none of the high-performing polymers studied has a dielectric constant value larger than 3, all polymer–fullerene blends have a significantly larger dielectric constant compared to their pristine constituents. Additionally, it is found that the blend dielectric constant reaches a maximum value in fully optimized devices. Using PTB7:PC71BM blends as an example, it is showed that, in addition to a small increase in the dielectric constant, devices fabricated using the optimum processing additive concentration exhibit almost 3X larger excited state polarizability. This large increase in excited state polarizability results in a substantial difference in short-circuit current and ultimately device performance. The results show that the excited state polarizability critically depends on polymer–fullerene interactions, and can be a leading indicator of device performance for a given material system.

Effect of Polymer–Fullerene Interaction on the Dielectric Properties of the Blend

/pdf/critical-role-of-polymer-aggregation-and-miscibility-in-3zj4uyu5jt.pdf

Xueping Yi

Papers

Efficient Energy Funneling in Quasi-2D Perovskites: From Light Emission to Lasing

Ultraviolet-ozone surface modification for non-wetting hole transport materials based inverted planar perovskite solar cells with efficiency exceeding 18%

Impact of Nonfullerene Molecular Architecture on Charge Generation, Transport, and Morphology in PTB7-Th-Based Organic Solar Cells

Effect of Polymer–Fullerene Interaction on the Dielectric Properties of the Blend

Critical Role of Polymer Aggregation and Miscibility in Nonfullerene-Based Organic Photovoltaics