Comprehensive design ideas on the fused-ring donor-core in state-of-the-art acceptor-donor-acceptor (A-D-A) nonfullerene acceptors (NFAs) are still of great importance for regulating the electron push-pull effect for the sake of optimal light-harvesting, frontier molecular orbital levels, and finally their photovoltaic properties. Herein, thieno[3,2-b]thiophenes were fused in bay-area of naphthalene via six-member-ring connection, resulting in the formation of dihydropyrenobisthieno[3,2-b]thiophene based octacyclic ladder-type donor core, which was flanked by two 1,1-dicyanomethylene-3-indanone (IC) acceptor motifs with and without 5,6-diflourination, namely PTT-IC and PTT-2FIC, respectively, as novel efficient A-D-A fused-ring electron acceptors (FREAs). Compared with PTT-IC, fluorinated PTT-2FIC possesses narrower optical bandgap of 1.48 eV, better pi-pi stacking, and its PBDB-T:PTT-2FIC blend film exhibited better morphology, and better hole and electron mobility. As a result, nonfullerene solar cells using PBDB-T:PTT-2FIC as the active layer achieved a decent PCE of 10.40%, with an open-circuit voltage (V-OC) of 0.87 V, a fill factor (FF) of 0.65, and a much higher short-circuit current (J(SC)) of 18.26 mA/cm(2). Meanwhile, the PBDB-T:PTT-IC cells delivered a lower J(SC) of 12.58 mA/cm(2) but a higher V-OC of 0.99 V, thus resulting in a PCE of 7.39% due to its wider optical bandgap of 1.58 eV and higher LUMO energy level. These results demonstrated that NFAs based on fused-ring donor core from fusing thieno [3,2-b]thiophenes with naphthalene via six-member-ring connection are promising for organic photovoltaic applications.

In this work, the first diketopyrrolopyrrole (DPP) based donor-acceptor macrocyclic conjugated molecule was developed and its application in organic electronics was systematically studied. Macrocyclic molecules, as a fragment of armchair carbon nanotubes, have emerged as functional materials in materials chemistry, but the materials are always limited to cycloparaphenylenes. Using the donor-acceptor design strategy that has been widely used in high performance conjugated polymers for macrocyclic molecules, it will significantly broaden their species with tunable optical and electrical properties. Herein, we synthesize a well-defined macrocyclic molecule containing four electron-deficient DPP units alternating with electron-rich thiophenes. The new molecule was found to show high solubility, near-infrared absorption spectra and 3D charge transport properties. The new macrocyclic molecule as an electron acceptor was applied to non-fullerene organic solar cells, exhibiting an initial efficiency of 0.49%, while the linear molecule with a similar backbone only showed a very low efficiency of 0.03%. Our results demonstrate that donor-acceptor macrocyclic conjugated materials have great potential application in organic electronics.

Unveiling the correlations among molecular structures, morphological characteristics, macroscopic properties and device performances is crucial for developing better photovoltaic materials and achieving higher efficiencies. To achieve this goal, a comprehensive study is performed based on four state-of-the-art non-fullerene acceptors (NFAs), which allows to systematically examine the above-mentioned correlations from different scales. Its found that extending conjugation of NFA shows positive effects on charge separation promotion and non-radiative loss reduction, while asymmetric terminals can maximize benefits from both terminals. Another molecular optimization is from alkyl chain tuning. The shortened alkyl side chain results in strengthened terminal packing and decreased pi-pi distance, which contribute high carrier mobility and finally the high charge collection efficiency. With the most-acquired benefits from molecular structure and macroscopic factors, PM6:BTP-S9-based organic photovoltaics (OPVs) exhibit the optimal efficiency of 17.56% (certified: 17.4%) with a high fill factor of 78.44%, representing the best among asymmetric acceptor based OPVs. This work provides insight into the structure-performance relationships, and paves the way toward high-performance OPVs via molecular design. Understanding correlations between molecular structures and macroscopic properties is critical in realising highly efficient organic photovoltaics. Here, the authors conduct a comprehensive study based on four non-fullerene acceptors revealing how the extended conjugation, asymmetric terminals and alkyl chain length can affect device performance.

Sub-picosecond hole transfer has been recently observed in several narrow band gap nonfullerene small-molecule acceptor (NFA)-based binary blended organic solar cell (OSC) systems operating with negligible energetic driving forces. As the driving forces are near zero, how the added acceptor/donor guests tune the barrier-free hole-transfer dynamics of these systems remains very unclear. In this study, we report a new NFA (BTCT-2Cl) that conducts a sub-picosecond hole transfer (2 ps) for efficient photocurrent generation when pairing with PM6 though the energetic offset is only 0.02 eV. We observe that the added nonfullerene and PCBM components differently tune the charge generation and recombination when selectively exciting BTCT-2Cl. After adding PC71BM, the hole transfer from the host BTCT-2Cl to the host donor is greatly accelerated, with the rate significantly reduced to 0.29 ps and the charge generation becomes more efficient; on the contrary, recombination is prolonged and a larger fill factor is obtained after adding an NFA guest, here, IT-4F. The different tuning on the host binary hole-transfer dynamics is likely related with the phase crystallinity and the domain size changed after adding different acceptor guests. Over 16% efficiency is obtained on the PC71BM-based ternary device that outperforms the host binary and the IT-4F-based ternary solar cells (both showing over 15% efficiencies). The results clearly demonstrate that adding PCBM or NFA guests enables a very effective and different tuning on the hole-transfer rates and the recombination rates between the barrier-free host binary components, hence leading to efficient tuning on the short-circuit current density and fill factor, which outlines new strategies toward designing high-efficiency ternary blended OSC systems.

Multi-component organic photovoltaics (OPVs), e.g., ternary blends, are effective for high performance, while the fundamental understanding from the molecular to device level is lacking. To address this issue, we here systematically study the working mechanism of ternary OPVs based on non-fullerene acceptors (NFAs). With both molecular dynamics simulations and morphology characterization, we identify that when adding another larger band gap and highly miscible NFA, namely IT-4F or BTP-S2, into the PBDB-TF:BTP-eC9 blend, the NFAs undergo molecular intermixing selectively with BTP-eC9. This causes the composition-dependent band gap and charge recombination, and hence the composition-dependent V-OC. While the charge recombination still dominantly occurs at the PBDB-TF:BTP-eC9 interface, BTP-S2 or IT-4F plays an auxiliary role in facilitating charge transfer and suppressing non-radiative decay. Interestingly, intermolecular end-group packing in the intermixed blend is improved compared to that in pristine films, leading to higher carrier mobility. These synergistic effects significantly improve the power conversion efficiency of the device to an outstanding value of 18.7% (certified value of 18.3%).

We report a faster rate of hole transfer under a smaller AHomo in a comparative study of two group organic solar cells (OSCs) consisting of IT-4F as an acceptor and PBDBT and PBDBT-SF as donors. In the OSCs based on PBDBT. SF:IT-4F, a higher short-circuit current (J(SC)) was observed with a Delta(Homo) of 0.31 eV compared to a lower Jsc in PBDBT:IT-4F OSCs with a larger Delta(Homo) (0.45 eV). Intensive investigation indicates that the rate of transfer of a hole from IT-4F to PBDBT-SF or PBDBT is inversely proportional to the Delta(Homo) between IT-4F and donors. The larger Jsc in the PBDBT-SF:IT-4F device is attributed to a synergy of faster hole transfer, slower recombination, and rapid charge extraction enabled by desired morphology and balanced charge carrier mobilities with PBDBT-SF, suggesting that under a sufficiently high Delta(Homo), comprehensive considerations of the transport, film morphology, and energy levels are needed when designing new materials for high-performance OSCs.

Fill factor (FF) is a determining parameter for the power conversion efficiency (PCE) of organic solar cells (OSC). So far, nonfullerene (NF) OSCs with state-of-the-art PCEs exhibit FFs <0.8, lower than the values of Si or perovskite solar cells. The FFs directly display the dependence of photocurrent on bias, meaning that the competition between charge extraction and recombination is modulated by internal electric potential (V-in). Here, we report a study to understand key parameters/properties affecting the device FF based on seven groups of NF-OSCs consisting of widely used PBDBT-2F or PTB7-Th donors and representative NF-acceptors with FFs ranging from 0.60 to 0.78 and PCEs from 10.27 to 16.09%. We used field-dependent transient photocurrent measurements to reveal that fast and field-insensitive charge extraction at low V-in is an essential prerequisite for obtaining high FFs (0.75-0.8), which is enabled by balanced charge transport in steady and reduced bimolecular charge recombination in high purity phases. With bias-dependent quantum efficiency analysis, we further show that the recombination loss at low V-in in the devices with low FFs tends to be more significant involving excitons generated in the donor phase of blends. Our results provide relevance for how to improve the FF toward the boost of photovoltaic performance in NF-OSCs.

The bulk heterojunction (BHJ) morphology of photovoltaic materials is crucial to the fundamental optoelectronic properties of organic solar cells (OSCs). However, in the photoactive layer, the intrinsic crystalline packing structure of Y6, currently the hallmark molecule among Y-series non-fullerene acceptors (NFAs), has not been unambiguously determined. Here, employing grazing-incidence wide-angle X-ray scattering (GIWAXS), we managed to uncover the intrinsic crystalline packing structure of Y6 in the BHJ active layer of OSCs, which is found to be different from its single-crystal structure reported previously. Moreover, we find that solvent additive 1-chloronaphthalene (CN) can induce highly ordered packing of Y6 in BHJ thin films. With the help of atomistic molecular dynamics simulations, it is revealed that pi-pi interactions generally exist between naphthalene derivatives and IC terminals of Y6 analogues, which would essentially improve their long-range ordering. Our work reveals the intrinsic crystalline packing structure of Y6 in the BHJ active layer as well as its crystallization mechanism in thin films, thus providing direct correlations between this crystalline packing and the device characteristics and photophysical properties.

Molecular weight (M-n) and conjugation of polymers can profoundly influence the performance of all-polymer solar cells (all-PSCs) via nanostructures of bulk heterojunctions (BHJs). To study the correlation between M-n and the performance of all-PSCs based on an acceptor with a flexible conjugation-break spacer (FCBS), three batches of acceptors, named PYTS, were synthesized with different number-average M-n from 9, 13 to 19 kDa. Blends with a polymer donor PBDB-T, the all-PSCs based on PYTS with M-n of 9 kDa and 19 kDa, exhibit power conversion efficiencies (PCEs) of 5.99% and 9.43%, respectively, primarily due to the increased short-circuit current density (J(sc)) from 13.02 to 18.73 mA cm(-2). To disclose the impact of M-n on device performance, dynamics of mixed PBDB-T:PYTS solutions to solid BHJs is studied by monitoring the drying process with home-made in situ multifunctional spectroscopy, which demonstrates that PYTS with M-n of 19 kDa has a longer drying time than the PYTS with M-n of 9 kDa. Prolonged drying of the BHJs with higher M-n PYTS facilitates more tightly packed structures with higher crystallinity. A systematic investigation on the nanostructures of BHJs, charge generation, transport and recombination is carried out with grazing-incidence wide-angle X-ray scattering (GIWAXS), transient absorption spectroscopy (TAS) and characterization of all-PSCs. The results indicate that increased crystallinity in the BHJs benefits exciton dissociation, electron transport, prolonged carrier lifetimes, and decreased non-geminate recombination rate constants in the corresponding devices. Combining the in situ study of drying and the investigation on films and devices provides us a comprehensive understanding of the interplay between M-n, the drying process, the nanostructures of BHJs and device performance. This work not only emphasizes the essential role of M-n in governing the device performance, but also exhibits recorded film formation through the in situ spectroscopy, enabling us to manipulate the nanostructure of BHJs by optimizing M-n of polymers and processing parameters.

Organic solar cells (OSCs) have attracted great attention due to their low cost, flexibility and solution-processibility. In recent years, the development of nonfullerene acceptors (NFAs) has truly promoted the efficiency of OSCs up to 19%, implying high potential for commercial applications. However, the stateof- the-art OSCs still lag behind the Shockley-Queisser limit, besides the intrinsic losses, understanding the extrinsic losses during charge generation, transport and extraction in devices is necessary.

The short-circuit current (J_SC) and open-circuit voltage (V_OC) can be simultaneously optimized in OSCs by tuning the energy levels of NFAs. However, less attention has been paid to the fill factor (FF), a crucial parameter for device efficiency. The FF reflects how the output photocurrent changes for a solar cell with a load from zero to infinity, indicating the charge extraction capability. In this thesis, the roles of energy offset, electric field, disorder and morphology on charge carrier dynamics as well as how these factors influence FF and energy loss are introduced. It is observed that fast and field-insensitive charge extraction is essential for high FF, which can be enabled by balanced transport and reduced bimolecular recombination. Additionally, the correlation between FF and voltage loss are studied based on four NFA systems with different highest occupied molecular orbital (HOMO) offsets. Larger HOMO offset could suppress hole back transfer from donor to acceptor and then lead to a larger FF, but it also induces more voltage loss.

The morphology of the active layer governs the charge dynamics and device performance. A comparative study based on all-polymer solar cells processed from chlorobenzene (CB) and o-Xylene has been performed. Film formation process and morphology characteristics demonstrate that CB-cast films exhibit better donor/acceptor miscibility and relatively ordered structure, yielding good device performance. Contrary, in o-Xylene cast devices, electron trapping leads to a smaller FF and more non-radiative recombination.

The state-of-the-art OSCs usually require comparable donor/acceptor contents in bulk-heterojunctions. Herein, NFA’s contribution to hole transport is investigated in dilute donor solar cells (10 wt% PM6:Y6). Comparable hole mobilities of PM6 diluted in Y6 and insulators (PS &PMMA) indicate that the hole transport in dilute donor solar cells is still mainly via PM6 phases, although pristine Y6 can support ambipolar transport. Furthermore, impressive performance of the dilute donor solar cells motivate us to explore semitransparent OSCs for building-integrated photovoltaics (BIPV). Decent photovoltaic performance and acceptable visible transparency have been realized in dilute donor solar cells by decreasing visible-absorption and increasing near-infrared absorption.

All-polymer solar cells (all-PSCs) have achieved impressive progress by employing acceptors polymerized from well performing small-molecule non-fullerene acceptors. Herein, the device performance and morphology evolution in blade-coated all-PSCs based on PBDBT:PF5-Y5 blends prepared from two different solvents, chlorobenzene (CB), and ortho-xylene (o-XY) are studied. The absorption spectra in CB solution indicate more ordered conformation for PF5-Y5. The drying process of PBDBT:PF5-Y5 blends is monitored by in situ multifunctional spectroscopy and the final film morphology is characterized with ex situ techniques. Finer-mixed donor/acceptor nanostructures are obtained in CB-cast film than that in o-XY-cast ones, corresponding to more efficient charge generation in the solar cells. More importantly, the conformation of polymers in solution determines the overall film morphology and the device performance. The relatively more ordered structure in CB-cast films is beneficial for charge transport and reduced non-radiative energy loss. Therefore, to achieve high-performance all-PSCs with small energy loss, it is crucial to gain favorable aggregation in the initial stage in solution.

The donor/acceptor weight ratio is crucial for photovoltaic performance of organic solar cells (OSCs). Here, we systematically investigate the photovoltaic behaviors of PM6:Y6 solar cells with different stoichiometries. It is found that the photovoltaic performance is tolerant to PM6 contents ranging from 10 to 60 wt %. Especially an impressive efficiency over 10% has been achieved in dilute donor solar cells with 10 wt % PM6 enabled by efficient charge generation, electron/ hole transport, slow charge recombination, and field-insensitive extraction. This raises the question about the origin of efficient hole transport in such dilute donor structure. By investigating hole mobilities of PM6 diluted in Y6 and insulators, we find that effective hole transport pathway is mainly through PM6 phase in PM6:Y6 blends despite with low PM6 content. The results indicate that a low fraction of polymer donors combines with near-infrared nonfullerene acceptors could achieve high photovoltaic performance, which might be a candidate for semitransparent windows.

Semitransparent organic solar cells (ST-OSCs) are promising candidates for applications in building-integrated photovoltaics (BIPV) as windows and facades. The challenge to achieve highly efficient ST-OSCs is the trade-off between power conversion efficiency (PCE) and average visible transmittance (AVT). Herein, solution-processed ST-OSCs are demonstrated on the basis a polymer donor, PM6, and a small molecule acceptor, Y6; lowering the visible-absorbing PM6 contents in blends could increase AVT and maintain PCE. Additionally, conductive polymer PEDOT:PSS is used as the top electrode due to its high transparency, good conductivity, and solution processability. Efficient ST-OSCs with 20 wt % PM6 achieve high PCE of 7.46% and AVT of 36.4%. The light utilization efficiency (LUE) of 2.72% is among the best reported values for solution-processed ST-OSCs. This work provides a straightforward approach for solution-processed ST-OSCs by combining a low fraction of visible-wavelength-selective polymer donors with near-infrared nonfullerene acceptors to achieve high PCE and AVT simultaneously.

Fill factor (FF) is an important parameter governing the power conversion efficiency (PCE) in non-fullerene organic solar cells (NF-OSCs), which however is less studied than the other two parameters (short-circuit current J(sc) and open-circuit voltage V-oc). To understand how energy offsets, exciton and charge carrier dynamics impact the FF, four groups of bulk heterojunctions (BHJs) NF-OSCs are investigated with FFs varying from 0.61 to 0.78 under progressive changes of HOMO-HOMO offsets (Delta(HOMOs), from 0.09 to 0.24 eV). By pump-probe optical spectroscopy, we find that the FF exhibits a positive dependence on Delta(HOMO) and charge-separated state lifetime (tau(CS)) in the blends, a result of inhibited back charge transfers and recombination at the donor-acceptor interface under higher Delta(HOMO)s. Moreover, we observe a fast charge extraction with decreased sensitivity to internal electric-fields in high-FF devices. Despite these merits, the gains of FF are at the expense of increasing the voltage loss to non-radiative recombination in our studied systems. The combined results suggest that remaining appropriate energetic offsets is essential for controlling the carrier dynamics with longer-lived CS-states, restraining charge back transfer and reducing charge recombination toward high FFs and photovoltaic efficiencies.