以昇陳

Nature Communications, Published online: 14 May 2019; doi:10.1038/s41467-019-10098-z

Non-fullerene electron acceptors have pushed the efficiency of organic solar cells up to 15% but they all contain fused rings and are inconvenient to synthetic access. Here Yu et al. develop fully unfused acceptors featuring non-covalent intramolecular interactions, high efficiencies and high stability.

A series of polycyclic aromatic hydrocarbon (PAH) cores with distinct π‐conjugation size are incorporated to construct a new family of fused‐ring electron acceptors (FREAs) via a simple and low‐cost synthetic route. The optoelectronic properties can be fine‐tuned at a molecular level over a wide range, which enables pyrene‐based DTP‐IC‐4Ph achieving a promising power conversion efficiency (PCE) of 10.37% in additive‐free nonfullerene organic solar cells.

Abstract

A series of polycyclic aromatic hydrocarbons (PAHs) with extended π‐conjugated cores (from naphthalene, anthracene, pyrene, to perylene) are incorporated into nonfullerene acceptors for the first time. Four different fused‐ring electron acceptors (FREAs), i.e., DTN‐IC‐2Ph, DTA‐IC‐3Ph, DTP‐IC‐4Ph, and DTPy‐IC‐5Ph, are prepared via simple and facile synthetic procedures, yielding a remarkable platform to study the structure–property relationship for nonfullerene solar cells. With the PAH core being extended systematically, the gradually redshifted absorption with enhanced molar extinction coefficient (ε) is realized, the energy level of the highest occupied molecular orbital is up‐shifted, and the electron mobility is greatly enhanced. Meanwhile, the solubility decreases and the molecular packing becomes strengthened. As a result, with an optimized combination of these characteristics, DTP‐IC‐4Ph attains good solubility, high molar extinction coefficient, complementary absorption, suitable morphology, well‐matched energy levels, as well as efficient charge dissociation and transport in blend film. Consequently, the DTP‐IC‐4Ph‐based solar cells with a donor polymer, poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene))‐alt‐(5,5‐(1′,3′‐di‐2‐thienyl‐5′,7′‐bis(2‐ethylhexyl)benzo[1′,2′‐c:4′,5′‐c′]dithiophene‐4,8‐dione))] (PBDB‐T) exhibit a promising power conversion efficiency of 10.37% without any additives, which is close to the best performance achieved in additive‐free nonfullerene solar cells (NFSCs). The results demonstrate that the PAH building blocks have great potential for the construction of novel FREAs for efficient additive‐free NFSCs.

The coulomb binding energy of an electron and a hole on adjacent chromophores is in the order of 0.5 eV, yet for efficient solar cells, very little activation energy is required for the photodissociation of excitations. It is shown here how the combined effects of interfacial electrostatics, wave function delocalization, and disorder can account for this.

Abstract

The high efficiencies reported for organic solar cells and an almost negligible thermal activation measured for the photogeneration of charge carriers have called into question whether photoinduced interfacial charge transfer states are bound by a significant coulomb attraction, and how this can be reconciled with very low activation energies. Here, this question is addressed in a combined experimental and theoretical approach. The interfacial binding energy of a charge‐transfer state in a blend of MeLPPP:PCBM is determined by using energy resolved electrochemical impedance spectroscopy and is found to be about 0.5 eV. Temperature‐dependent photocurrent measurements on the same films, however, give an activation energy that is about one order of magnitude lower. Using analytical calculations and Monte Carlo simulation the authors illustrate how i) interfacial energetics and ii) transport topology reduce the activation energy required to separate the interfacial electron–hole pair, with about equal contributions from both effects. The activation energy, however, is not reduced by entropy, although entropy increases the overall photodissociation yield.

Symmetry breaking provides a new material design strategy for nonfullerene small molecule acceptors (SMAs). The past 10 years have witnessed significant advances in asymmetric nonfullerene SMAs in organic solar cells (OSCs). In this review, the progress of asymmetric nonfullerene SMAs is reviewed. The structure–property relationships and the perspectives for future development of asymmetric non‐fullerene SMAs are also discussed.

Abstract

Symmetry breaking provides a new material design strategy for nonfullerene small molecule acceptors (SMAs). The past 10 years have witnessed significant advances in asymmetric nonfullerene SMAs in organic solar cells (OSCs) with power conversion efficiency (PCE) increasing from ≈1% to ≈14%. In this review, the progress of asymmetric nonfullerene SMAs, including early reports of asymmetric nonfullerene SMAs, asymmetric PDI‐based nonfullerene SMAs, and asymmetric acceptor–donor–acceptor (A–D–A)‐type nonfullerene SMAs, is summarized. The structure–property relationships and the perspectives for future development of asymmetric nonfullerene SMAs are also discussed.

Embracing perovskite grains in a soft fullerene network represents a new and scalable approach, to make perovskite mechanically stable and thus compatible with flexible substrates. The method is demonstrated to prepare flexible perovskite solar cells with the highest ever reported power conversion efficiency. The superior mechanical stability from device performance under working conditions is characterized in situ.

Abstract

Halide perovskite films processed from solution at low‐temperature offer promising opportunities to make flexible solar cells. However, the brittleness of perovskite films is an issue for mechanical stability in flexible devices. Herein, photo‐crosslinked [6,6]‐phenylC₆₁‐butyric oxetane dendron ester (C‐PCBOD) is used to improve the mechanical stability of methylammonium lead iodide (MAPbI₃) perovskite films. Also, it is demonstrated that C‐PCBOD passivates the grain boundaries, which reduces the formation of trap states and enhances the environmental stability of MAPbI₃. Thus, MAPbI₃ perovskite solar cells are prepared on solid and flexible substrates with record efficiencies of 20.4% and 18.1%, respectively, which are among the highest ever reported for MAPbI₃ on both flexible and solid substrates. The result of this work provides a step improvement toward stable and efficient flexible perovskite solar cells.

A novel dimeric n‐dopant (N‐DMBI)₂, is designed and synthesized to understand the effects of molecular dopants on thermoelectric properties. This study shows how the counterion shape, and the doping mechanism affect the thermoelectric performance and the transport pathway of n‐type conducting polymers, and reveals what type of n‐dopant is preferable.

Abstract

Molecular doping is a powerful method to fine‐tune the thermoelectric properties of organic semiconductors, in particular to impart the requisite electrical conductivity. The incorporation of molecular dopants can, however, perturb the microstructure of semicrystalline organic semiconductors, which complicates the development of a detailed understanding of structure–property relationships. To better understand how the doping pathway and the resulting dopant counterion influence the thermoelectric performance and transport properties, a new dimer dopant, (N‐DMBI)₂, is developed. Subsequently, FBDPPV is then n‐doped with dimer dopants (N‐DMBI)₂, (RuCp*mes)₂, and the hydride‐donor dopant N‐DMBI‐H. By comparing the UV–vis–NIR absorption spectra and morphological characteristics of the doped polymers, it is found that not only the doping mechanism, but also the shape of the counterion strongly influence the thermoelectric properties and transport characteristics. (N‐DMBI)₂, which is a direct electron‐donating dopant with a comparatively small, relatively planar counterion, gives the best power factor among the three systems studied here. Additionally, temperature‐dependent conductivity and Seebeck coefficient measurements differ between the three dopants with (N‐DMBI)₂ yielding the best thermoelectric properties. The results of this study of dopant effects on thermoelectric properties provide insight into guidelines for future organic thermoelectrics.

A series of polycyclic aromatic hydrocarbon (PAH) cores with distinct π‐conjugation size are incorporated to construct a new family of fused‐ring electron acceptors (FREAs) via a simple and low‐cost synthetic route. The optoelectronic properties can be fine‐tuned at a molecular level over a wide range, which enables pyrene‐based DTP‐IC‐4Ph achieving a promising power conversion efficiency (PCE) of 10.37% in additive‐free nonfullerene organic solar cells.

Abstract

A series of polycyclic aromatic hydrocarbons (PAHs) with extended π‐conjugated cores (from naphthalene, anthracene, pyrene, to perylene) are incorporated into nonfullerene acceptors for the first time. Four different fused‐ring electron acceptors (FREAs), i.e., DTN‐IC‐2Ph, DTA‐IC‐3Ph, DTP‐IC‐4Ph, and DTPy‐IC‐5Ph, are prepared via simple and facile synthetic procedures, yielding a remarkable platform to study the structure–property relationship for nonfullerene solar cells. With the PAH core being extended systematically, the gradually redshifted absorption with enhanced molar extinction coefficient (ε) is realized, the energy level of the highest occupied molecular orbital is up‐shifted, and the electron mobility is greatly enhanced. Meanwhile, the solubility decreases and the molecular packing becomes strengthened. As a result, with an optimized combination of these characteristics, DTP‐IC‐4Ph attains good solubility, high molar extinction coefficient, complementary absorption, suitable morphology, well‐matched energy levels, as well as efficient charge dissociation and transport in blend film. Consequently, the DTP‐IC‐4Ph‐based solar cells with a donor polymer, poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene))‐alt‐(5,5‐(1′,3′‐di‐2‐thienyl‐5′,7′‐bis(2‐ethylhexyl)benzo[1′,2′‐c:4′,5′‐c′]dithiophene‐4,8‐dione))] (PBDB‐T) exhibit a promising power conversion efficiency of 10.37% without any additives, which is close to the best performance achieved in additive‐free nonfullerene solar cells (NFSCs). The results demonstrate that the PAH building blocks have great potential for the construction of novel FREAs for efficient additive‐free NFSCs.

Publication date: June 2019

Source: Materials Today Energy, Volume 12

Author(s): Ershuai Jiang, Jin Yan, Yuqian Ai, Nan Li, Baojie Yan, Yuheng Zeng, Jiang Sheng, Jichun Ye

Graphical abstract

Enhancing the performance of pure organic room-temperature phosphorescent luminophores

Enhancing the performance of pure organic room-temperature phosphorescent luminophores, Published online: 08 May 2019; doi:10.1038/s41467-019-10033-2

Pure organic molecules displaying room-temperature phosphorescence (RTP) are a rapidly emerging class of luminophores. In this Review, the authors discuss the principles for their rational design and development, from the underlying photophysical mechanisms of organic RTP, to enhancement and processing strategies for their practical application.

Nature Chemistry, Published online: 06 May 2019; doi:10.1038/s41557-019-0264-3

The reaction between an excited atom and a charged molecule has now been studied at low temperature and a reaction blockading effect has been observed that differs significantly from what is expected from standard chemical capture theory.