Jiangbin Zhang

What Controls the Rate of Ultrafast Charge Transfer and Charge Separation Efficiency in Organic Photovoltaic Blends

In solar energy harvesting devices based on molecular semiconductors, such as organic photovoltaics (OPVs) and artificial photosynthetic systems, Frenkel excitons must be dissociated via charge transfer at heterojunctions to yield free charges. What controls the rate and efficiency of charge transfer and charge separation is an important question, as it determines the overall power conversion efficiency (PCE) of these systems. In bulk heterojunctions between polymer donor and fullerene acceptors, which provide a model system to understand the fundamental dynamics of electron transfer in molecular systems, it has been established that the first step of photoinduced electron transfer can be fast, of order 100 fs. But here we report the first study which correlates differences in the electron transfer rate with electronic structure and morphology, achieved with sub-20 fs time resolution pump-probe spectroscopy. We vary both the fullerene substitution and donor/fullerene ratio which allow us to control both aggregate size and the energetic driving force for charge transfer. We observe a range of electron transfer times from polymer to fullerene, from 240 fs to as short as 37 fs. Using ultrafast electro-optical pump-push-photocurrent spectroscopy, we find the yield of free versus bound charges to be weakly dependent on the energetic driving force, but to be very strongly dependent on fullerene aggregate size and packing. Our results point toward the importance of state accessibility and charge delocalization and suggest that energetic offsets between donor and acceptor levels are not an important criterion for efficient charge generation. This provides design rules for next-generation materials to minimize losses related to driving energy and boost PCE.

Fine-Tuning the Energy Levels of a Nonfullerene Small-Molecule Acceptor to Achieve a High Short-Circuit Current and a Power Conversion Efficiency over 12% in Organic Solar Cells.

Organic solar cell optimization requires careful balancing of current-voltage output of the materials system. Here, such optimization using ultrafast spectroscopy as a tool to optimize the material bandgap without altering ultrafast photophysics is reported. A new acceptor-donor-acceptor (A-D-A)-type small-molecule acceptor NCBDT is designed by modification of the D and A units of NFBDT. Compared to NFBDT, NCBDT exhibits upshifted highest occupied molecular orbital (HOMO) energy level mainly due to the additional octyl on the D unit and downshifted lowest unoccupied molecular orbital (LUMO) energy level due to the fluorination of A units. NCBDT has a low optical bandgap of 1.45 eV which extends the absorption range toward near-IR region, down to ≈860 nm. However, the 60 meV lowered LUMO level of NCBDT hardly changes the Voc level, and the elevation of the NCBDT HOMO does not have a substantial influence on the photophysics of the materials. Thus, for both NCBDT- and NFBDT-based systems, an unusually slow (≈400 ps) but ultimately efficient charge generation mediated by interfacial charge-pair states is observed, followed by effective charge extraction. As a result, the PBDB-T:NCBDT devices demonstrate an impressive power conversion efficiency over 12%-among the best for solution-processed organic solar cells.

On the energetics of bound charge-transfer states in organic photovoltaics

A comprehensive understanding of the charge generation mechanism in organic solar cells is critical for further improvement of device performance. Currently, the origin and magnitude of the coulombic binding energy of the charge-transfer state (CTS), an intermediate state which is fundamental for the charge separation process, are still under debate. Here, we propose a new approach for determining the dissociation energy of localised CTSs for a range of devices with different alignments of molecular energy levels (tuned by chemical modifications of fullerene) and disorder (adjusted by the blend composition) using temperature-dependent pump-push photocurrent spectroscopy. We observe that the dissociation of localised CTSs from initial excitation is a temperature-dependent process, and we determined the binding energy of these CTSs by measuring a single activation energy over a wide temperature range. We propose a simple qualitative picture to explain the observation, based on the split between the bound CTSs and free charges. In all the material systems studied here, the activation energy falls within the range of 90 ± 50 meV (corresponding to ∼1 nm separation of an electron–hole pair). Surprisingly, the binding energy does not depend on the material composition or the driving energy (∼150 meV variation) for charge separation. In contrast, the number of formed bound states and their following recombination dynamics are material- and nanomorphology-sensitive. Such observations in the studied benchmark polymer:fullerene systems reveal unexpected similarities in the energetics of CTSs formed in different electronic environments. This makes our results of general importance for understanding the photophysics at the heterojunction interface and for further development of organic photovoltaics.

Design rules for minimizing voltage losses in high-efficiency organic solar cells

The open-circuit voltage of organic solar cells is usually lower than the values achieved in inorganic or perovskite photovoltaic devices with comparable bandgaps. Energy losses during charge separation at the donor–acceptor interface and non-radiative recombination are among the main causes of such voltage losses. Here we combine spectroscopic and quantum-chemistry approaches to identify key rules for minimizing voltage losses: (1) a low energy offset between donor and acceptor molecular states and (2) high photoluminescence yield of the low-gap material in the blend. Following these rules, we present a range of existing and new donor–acceptor systems that combine efficient photocurrent generation with electroluminescence yield up to 0.03%, leading to non-radiative voltage losses as small as 0.21 V. This study provides a rationale to explain and further improve the performance of recently demonstrated high-open-circuit-voltage organic solar cells.Key optoelectronic properties for donor and acceptor organic semiconductors are identified to obtain organic solar cells with reduced open-circuit voltage losses and high power conversion efficiencies.

Control of Geminate recombination by the material composition and processing conditions in novel polymer: Nonfullerene Acceptor Photovoltaic devices

Herein, we report on the charge dynamics of photovoltaic devices based on two novel small-molecule nonfullerene acceptors featuring a central ketone unit. Using ultrafast near-infrared spectroscopy with optical and photocurrent detection methods, we identify one of the key loss channels in the devices as geminate recombination (GR) of interfacial charge transfer states (CTSs). We find that the magnitude of GR is highly sensitive to the choice of solvent and annealing conditions. Interestingly, regardless of these processing conditions, the same lifetime for GR (∼130 ps) is obtained by both detection methods upon decomposing the complex broadband transient optical spectra, suggesting this time scale is inherent and independent of morphology. These observations suggest that the CTSs in the studied material blends are mostly strongly bound, and that charge generation from these states is highly inefficient. We further rationalize our results by considering the impact of the processing on the morphology of the mixed donor and acceptor domains and discuss the potential consequences of the early charge dynamics on the performance of emerging nonfullerene photovoltaic devices. Our results demonstrate that careful choice of processing conditions enables enhanced exciton harvesting and suppression of GR by more than 3 orders of magnitude.

Efficient non-fullerene organic solar cells employing sequentially deposited donor–acceptor layers

Non-fullerene acceptors (NFAs) have recently outperformed their fullerene counterparts in binary bulk-heterojunction (BHJ) organic solar cells (OSCs). Further development of NFA OSCs may benefit other novel OSC device structures that alter or extend the standard BHJ concept. Here, we report such a new processing route that forms a BHJ-like morphology between sequentially processed polymer donor and NFA with high power conversion efficiencies in excess of 10%. Both devices show similar charge generation and recombination behaviours, supporting formation of similar BHJ active layers. We correlate the ∼30 meV smaller open-circuit voltage in sq-BHJ devices to more substantial non-radiative recombination by voltage loss analysis. We also determine the exciton diffusion length of benchmark polymer PBDB-T to be 10 ± 3 nm. Our results demonstrate high-efficiency OSC devices using sequential deposition method and provide new opportunities to further improve performance of state-of-the-art OSCs.

Molecular doping of single-walled carbon nanotube transistors: optoelectronic study

Single-walled carbon nanotubes (SWCNT) are a promising material for future optoelectronic applications, including flexible electrodes and field-effect transistors. Molecular doping of carbon nanotube surface can be an effective way to control the electronic structure and charge dynamics of these material systems. Herein, two organic semiconductors with different energy level alignment in respect to SWCNT are used to dope the channel of the SWCNT-based transistor. The effects of doping on the device performance are studied with a set of optoelectronic measurements. For the studied system, we observed an opposite change in photo-resistance, depending on the type (electron donor vs electron acceptor) of the dopants. We attribute this effect to interplay between two effects: (i) the change in the carrier concentration and (ii) the formation of trapping states at the SWCNT surface. We also observed a modest ~4 pA photocurrent generation in the doped systems, which indicates that the studied system could be used as a platform for multi-pulse optoelectronic experiments with photocurrent detection.

Monolayer organic field effect phototransistors: photophysical characterization and modeling

Оrganic field-effect transistors (OFET) can combine photodetection and light amplification and, for example, work as phototransistors. Such organic phototransistors can be used in light-controlled switches and amplifiers, detection circuits, and sensors of ultrasensitive images. In this work, we present photophysical characterization of well-defined ultrathin organic field-effect devices with a semiconductive channel based on Langmuir-Blodgett monolayer film. We observe clear generation of photocurrent under illumination with a modulated laser at 405 nm. The increase of photocurrent with the optical modulation frequency indicates the presence of defect states serving as traps for photogenerated carriers and/or the saturation of charge concentration in the thin active layer. We also propose a simple one-dimensional numerical model of a photosensitive OFET. The model is based on the Poisson, current continuity and drift-diffusion equations allows future evaluation of the photocurrent generation mechanism in the studied systems.