Hybridization of Local Exciton and Charge-Transfer States Reduces Nonradiative Voltage Losses in Organic Solar Cells.

A number of recent studies have shown that the nonradiative voltage losses in organic solar cells can be suppressed in systems with low energetic offsets between donor and acceptor molecular states, but the physical reasons underpinning this remain unclear. Here, we present a systematic study of 18 different donor/acceptor blends to determine the effect that energetic offset has on both radiative and nonradiative recombination of the charge-transfer (CT) state. We find that, for certain blends, low offsets result in hybridization between charge-transfer and lowest donor or acceptor exciton states, which leads to a strong suppression in the nonradiative voltage loss to values as low as 0.23 V associated with an increase in the luminescence of the CT state. Further, we extend a two-state CT-state recombination model to include the interaction between CT and first excited states, which allows us to explain the low nonradiative voltage losses as an increase in the effective CT to ground state oscillator strength due to the intensity borrowing mechanism. We show that low nonradiative voltage losses can be achieved in material combinations with a strong electronic coupling between CT and first excited states and where the lower band gap material has a high oscillator strength for transitions from the excited state to the ground state. Finally, from our model we propose that achieving very low nonradiative voltage losses may come at a cost of higher overall recombination rates, which may help to explain the generally lower FF and EQE of highly hybridized systems.

Structural Identification of 19 Purified Isomers of the OPV Acceptor Material bisPCBM by 13C NMR and UV-Vis Absorption Spectroscopy and High-Performance Liquid Chromatography.

The molecular structures of 19 purified isomers of bis-phenyl-C62-butyric acid methyl ester were identified by a combination of 13C NMR and UV-vis absorption spectroscopies and high-performance liquid chromatography (HPLC) retention time analysis. All 19 isomers are dicyclopropafullerenes (none are homofullerenes). There were seven isomers with C1 molecular point-group symmetry, four with C s, six with C2, one with C2 v, and one with C2 h symmetry. The C2 h, C2 v, and all five nonequatorial C1 isomers were unambiguously assigned to their respective HPLC fractions. For the other 12 isomers, the 13C NMR and UV-vis spectra placed them in six groups of two same-symmetry isomers. On the basis of the widely spaced HPLC retention times of the two isomers within each of these six groups, and the empirical inverse correlation between retention time and addend spacing, each isomer was assigned to its corresponding HPLC fraction. In addition, the missing trans-1 isomer was found, purified, and characterized.

Structure-Property Relationships for the Electronic Applications of Bis-Adduct Isomers of Phenyl-C61 Butyric Acid Methyl Ester.

Higher adducts of a fullerene, such as the bis-adduct of PCBM (bis-PCBM), can be used to achieve shallower molecular orbital energy levels than, for example, PCBM or C60. Substituting the bis-adduct for the parent fullerene is useful to increase the open-circuit voltage of organic solar cells or achieve better energy alignment as electron transport layers in, for example, perovskite solar cells. However, bis-PCBM is usually synthesized as a mixture of structural isomers, which can lead to both energetic and morphological disorder, negatively affecting device performance. Here, we present a comprehensive study on the molecular properties of 19 pure bis-isomers of PCBM using a variety of characterization methods, including ultraviolet photoelectron spectroscopy, thermal gravimetric analysis, differential scanning calorimetry, single crystal structure, and (time-dependent) density functional theory calculation. We find that the lowest unoccupied molecular orbital of such bis-isomers can be tuned to be up to 170 meV shallower than PCBM and up to 100 meV shallower than the mixture of unseparated isomers. The isolated bis-isomers also show an electron mobility in organic field-effect transistors of up to 4.5 × 10-2 cm2/(V s), which is an order of magnitude higher than that of the mixture of bis-isomers. These properties enable the fabrication of the highest performing bis-PCBM organic solar cell to date, with the best device showing a power conversion efficiency of 7.2%. Interestingly, we find that the crystallinity of bis-isomers correlates negatively with electron mobility and organic solar cell device performance, which we relate to their molecular symmetry, with a lower symmetry leading to more amorphous bis-isomers, less energetic disorder, and higher dimensional electron transport. This work demonstrates the potential of side chain engineering for optimizing the performance of fullerene-based organic electronic devices.

Hot electron production and diffuse excited states in C70, C82, and Sc3N@C80 characterized by angular-resolved photoelectron spectroscopy.

Angular-resolved photoelectron spectroscopy using wavelength-tuneable femtosecond laser pulses is presented for a series of fullerenes, namely, C70, C82, and Sc3N@C80. The photoelectron kinetic energy distributions for the three molecules show typical thermal electron spectra with a superimposed peak structure that is the result of one-photon ionization of diffuse low-angular momenta states with electron density close to the carbon cage and that are related to so-called super atom molecular orbitals. Photoelectron angular distributions confirm this assignment. The observed structure is less prominent compared to the thermal electron background than what was observed in C60. It can be concluded that hot electron emission is the main ionization channel for the larger and more complex molecules for these excitation conditions.

Relationship between molecular properties and degradation mechanisms of organic solar cells based on bis-adducts of phenyl-C61 butyric acid methyl ester.

Environmental stability remains a major challenge for the commercialisation of organic solar cells and degradation pathways remain poorly understood. Designing materials for improved device stability requires an understanding of the relationship between the properties of the donor or acceptor molecule and different degradation mechanisms. Here we study the correlations between various molecular parameters of the fullerene derivative bis-PCBM and the degradation rate of polymer:bis-PCBM organic solar cells, based on the same carbazole-alt-benzothiadiazole polymer, in aerobic and anaerobic conditions. We compare eight high purity bis-PCBM isomers with different electronic, chemical and packing properties along with PCBM and the mixture of bis isomers. In the case of aerobic photodegradation, we find that device degradation rate is positively correlated to the LUMO energy of the bis-PCBM isomer and to the degree of crystallinity of the isomer, while the correlation of degradation with driving force for epoxide formation is unclear. These results support the idea that in these samples, aerobic photodegradation proceeds via superoxide formation by the photogenerated polaron on the fullerene, followed by further chemical reaction. In the absence of air, photodegradation rate is correlated with molecular structure, supporting the mechanism of microstructural degradation via fullerene dimerization. The approach and findings presented here show how control of specific molecular parameters through chemical design can serve as a strategy to enhance stability of organic solar cells.

Fullerene Desymmetrization as a Means to Achieve Single-Enantiomer Electron Acceptors with Maximized Chiroptical Responsiveness.

Solubilized fullerene derivatives have revolutionized the development of organic photovoltaic devices, acting as excellent electron acceptors. The addition of solubilizing addends to the fullerene cage results in a large number of isomers, which are generally employed as isomeric mixtures. Moreover, a significant number of these isomers are chiral, which further adds to the isomeric complexity. The opportunities presented by single-isomer, and particularly single-enantiomer, fullerenes in organic electronic materials and devices are poorly understood however. Here, ten pairs of enantiomers are separated from the 19 structural isomers of bis[60]phenyl-C61-butyric acid methyl ester, using them to elucidate important chiroptical relationships and demonstrating their application to a circularly polarized light (CPL)-detecting device. Larger chiroptical responses are found, occurring through the inherent chirality of the fullerene. When used in a single-enantiomer organic field-effect transistor, the potential to discriminate CPL with a fast light response time and with a very high photocurrent dissymmetry factor (gph  = 1.27 ± 0.06) is demonstrated. This study thus provides key strategies to design fullerenes with large chiroptical responses for use as chiral components of organic electronic devices. It is anticipated that this data will position chiral fullerenes as an exciting material class for the growing field of chiral electronic technologies.

Conformational Analysis of [60]PCBM via Second-Order Proton NMR Spin-Spin Coupling Effects.

The 1H NMR spectrum of phenyl C61 butyric acid methyl ester ([60]PCBM) was recorded at high resolution (600 MHz). All of the 1H resonances expected of the Cs-symmetric molecule were observed. The spin-spin couplings in the 1H NMR spectrum were not as expected at first order. Instead, the effects of AA'BB'-type second-order couplings were clearly observed for the protons attached to both ester carbons C3 and C4, which were analyzed in terms of seven coupling constants. This indicates that there is no free rotation of the σ bonds of the alkyl chain in the ester group, although rotation becomes free at a larger distance from the fullerene bridge carbon (C61). The 1H NMR results further indicated that there is a 1:6:1 population ratio of the three staggered conformers (gauche:anti:gauche') about the ester group C3-C4 bond. These results may aid in the understanding of the morphological interactions between [60]PCBM and its surroundings in condensed-phase organic electronic devices such as organic and perovskite photovoltaics.

Capillary-written single-crystalline all-inorganic perovskite microribbon arrays for highly-sensitive and thermal-stable photodetectors.

In recent times, as a result of its exceptional resistance to moisture and heat, cesium lead bromide (CsPbBr3) has been established as a potential high-performance perovskite material for optoelectronics, which is inclusive of photodetectors and photovoltaics. It has been demonstrated that a perovskite single crystal has major benefits over its thin-film equivalents; nevertheless, the preparation of perovskite crystal arrays for the utilisation of extensive integration is a challenging task. In this paper, we consider a simple crystallisation system, being a capillary-written system to enable the growth of single crystal microribbon arrays (MRAs) directly from a precursor solution. It is demonstrated by microstructure characterisation that CsPbBr3 MRAs are good-quality single crystals with highly-aligned crystal packing and smooth surfaces. The band-edge photoluminescence (PL) is exceptionally resilient and has a lengthy PL life of ∼62 ns. An exceptional photo-response having a particularly quick 99 µs response time and a 2496 A W-1 ultra-high responsivity is exhibited by photodetectors which are built upon these MRAs. The fact that the as-fabricated photodetectors maintain 90% of their commencing performance following 100 days of constant stress testing under ambient conditions under an illumination of 450 nm, showing exceptional operational stability, is noteworthy. A significant step towards the large-area growth of high-quality perovskite MRAs is presented by this work. This supplies favourable opportunities to build high-performance optoelectronic and nanophotonic systems.

Organic Single-Crystalline p-n Heterojunctions for High-Performance Ambipolar Field-Effect Transistors and Broadband Photodetectors.

Organic semiconducting single crystals are ideal building blocks for organic field-effect transistors (OFETs) and organic photodetectors (OPDs) because they can potentially exhibit the best charge transport and photoelectric properties in organic materials. Nevertheless, it is usual for single-crystal OFETs to be built from one kind of organic material in which the dominant transport is either electron or hole; such OFETs show unipolar charge transport. Furthermore, single-crystal OPDs present high performance only in restricted regions because of the limited absorption of one-component single crystals. In an ideal situation, devices which comprise both electron- and hole-transporting single crystals with complementary absorptions, such as single-crystalline p-n heterojunctions (SCHJs), can permit broadband photoresponse and ambipolar charge transport. In this paper, a solution-processing crystallization strategy to prepare an SCHJ composed of C60 and 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-PEN) was shown. These SCHJs demonstrated ambipolar charge-transport characteristics in OFETs with a balanced performance of 2.9 cm2 V-1 s-1 for electron mobility and 2.7 cm2 V-1 s-1 for hole mobility. This demonstration is the first of single-crystal OFETs in which both electron and hole mobilities were over 2.5 cm2 V-1 s-1. OPDs fabricated upon as-prepared SCHJs exhibited highly sensitive photoconductive properties ranging from ultraviolet to visible and further to near-infrared regions as a result of complementary absorption between C60 and TIPS-PEN, thereby attaining photoresponsivities that are among the highest reported values within the OPDs. This work would provide valuable references for developing novel SCHJ systems to achieve significant progress in high-performance ambipolar OFETs and broadband OPDs.

Antisolvent-assisted controllable growth of fullerene single crystal microwires for organic field effect transistors and photodetectors.

There are only a few reported methods by which the size and morphology of organic single crystals for high-performance organic field-effect transistors (OFETs) or other devices can be controlled. Here, a facile solution-processed antisolvent vapor diffusion method was employed to grow millimeter-length C60 single crystal microwires directly in solution. The size of the microwires can be controllably varied via the C60 concentration and/or the choice of antisolvent. OFETs fabricated from the as-produced microwires exhibit mobilities as high as 2.30 cm2 V-1 s-1. A clear relationship between the crystal preparation conditions and device performance is revealed whereby it is observed that the lower the evaporation rate of antisolvent and/or the higher the C60 concentration, the higher the device performance. Photodetectors based on our microwires give a responsivity that is an order of magnitude higher than those grown by drop-casting methods. This study provides a facile method for the crystal engineering of size-tunable millimeter-length C60 single crystals, and revealed the important influences of the antisolvent on the C60 crystal size and the performance of devices based on them. We believe that our processing approach can be further exploited for a broad range of other organic semiconductors to achieve desirable single crystal size and morphology and thus obtain desirable OFETs and photodetector performance.

Isomer-Pure Bis-PCBM-Assisted Crystal Engineering of Perovskite Solar Cells Showing Excellent Efficiency and Stability.

A fullerene derivative (α-bis-PCBM) is purified from an as-produced bis-phenyl-C61 -butyric acid methyl ester (bis-[60]PCBM) isomer mixture by preparative peak-recycling, high-performance liquid chromatography, and is employed as a templating agent for solution processing of metal halide perovskite films via an antisolvent method. The resulting α-bis-PCBM-containing perovskite solar cells achieve better stability, efficiency, and reproducibility when compared with analogous cells containing PCBM. α-bis-PCBM fills the vacancies and grain boundaries of the perovskite film, enhancing the crystallization of perovskites and addressing the issue of slow electron extraction. In addition, α-bis-PCBM resists the ingression of moisture and passivates voids or pinholes generated in the hole-transporting layer. As a result, a power conversion efficiency (PCE) of 20.8% is obtained, compared with 19.9% by PCBM, and is accompanied by excellent stability under heat and simulated sunlight. The PCE of unsealed devices dropped by less than 10% in ambient air (40% RH) after 44 d at 65 °C, and by 4% after 600 h under continuous full-sun illumination and maximum power point tracking, respectively.

Purification by HPLC and the UV/Vis absorption spectra of the nitrogen-containing incar-fullerenes iNC60, and iNC70.

We report the purification of the nitrogen-containing incar-fullerenes iNC(60) and iNC(70), and their characterisation by UV-Vis absorption spectroscopy.