Adding a small-molecule donor (SMD) to state-of-the-art nonfullerene organic solar cells (OSCs) is demonstrated as a useful strategy to construct ternary organic solar cells, as SMDs typically have high crystallinity and can tune charge transport properties of OSCs. However, the absorption of most SMDs overlaps with typical donor polymers (e.g., PM6), which is against the general guidelines of adopting materials with complementary absorption in ternary OSCs. Herein, the absorption of state-of-art SMDs (BTR-CI) by linking the beta position of the outer thiophene to the alpha position of the inner thiophene unit is intentionally blueshifted. The resulting molecule beta-S1 shows a maximum absorption peak at 505 nm in the film state, which exhibits wider bandgap and shows complementary absorption with the host system (PM6:Y6). The corresponding ternary OSCs with 20%wt beta-S1 show significantly enhanced efficiency from 16.2% to 17.1% due to the increased short-circuit current (J(sc)) and improved fill factor (FF). Herein, an effective strategy to design SMDs with both wider bandgaps and higher crystallinity for high-performance ternary OSCs is presented.

Rationally utilizing and developing synthetic units is of particular significance for the design of high-performance non-fullerene small-molecule acceptors (SMAs). Here, a thieno[3,2-b]pyrrole synthetic unit was employed to develop a set of SMAs (ThPy1, ThPy2, ThPy3 and ThPy4) by changing the number or the position of the pyrrole ring in the central core based on a standard SMA of IT-4Cl, compared to which the four thieno[3,2-b]pyrrole-based acceptors exhibit bathochromic absorption and upshifted frontier orbital energy level due to the strong electron-donating ability of pyrrole. As a result, the polymer solar cells (PSCs) of the four thieno[3,2-b]pyrrole-based acceptors yield higher open-circuit voltage and lower energy loss relative to those of the IT-4Cl-based device. What is more, the ThPy3-based device achieves a power conversion efficiency (PCE) (15.3%) and an outstanding fill factor (FF) (0.771) that are superior to the IT-4Cl-based device (PCE = 12.6%, FF = 0.758). The ThPy4-based device realizes the lowest energy loss and the smallest optical band gap, and the ternary PSC device based on PM6:BTP-eC9:ThPy4 exhibits a PCE of 18.43% and a FF of 0.802. Overall, this work sheds light on the great potential of thieno[3,2-b]pyrrole-based SMAs in realizing low energy loss and high PCE. Four heteroheptacene-based acceptors using thieno[3,2-b]pyrrole building block were developed for the first time, and all the four acceptors-based devices realized high performance and low energy loss.

The power conversion efficiencies (PCEs) of organic solar cells (OSCs) have surpassed 19% thanks to the innovation of polymer donors and molecular acceptors. However, the batch-to-batch variations in polymer materials are detrimental to the reproducibility of the device performance. In comparison, small-molecule donors (SMDs) possess some unique advantages, such as well-defined molecular weights, easy purification, and excellent batch-to-batch repeatability. Herein, a pair of regioisomeric SMDs (BT-O1 and BT-O2) has been synthesized with alkoxy groups as S center dot center dot center dot O noncovalently conformational locks (NoCLs) at the inner and outer position, respectively. Theoretical and experimental results reveal that the regioisomeric effect has a significant influence on the light-harvest ability, energy levels, molecular geometries, internal reorganization energy, and packing behaviors for the two SMDs. As a result, BT-O2-based binary device shows an impressive PCE of 13.99%, much higher than that of BT-O1 based one (4.07%), due to the better-aligned energy level, more balanced charge transport, less charge recombination, lower energy loss, and more favorable phase separation. Furthermore, the fullerene derivative PC71BM is introduced into BT-O2:H3 as the third component to achieve a notable PCE of 15.34% (certified 14.6%). Overall, this work reveals that NoCLs is a promising strategy to achieve high-performance SMDs for all-small-molecule OSCs.

Organic solar cells (OSCs) are a next-generation photovoltaic technology that convert solar energy to electrical energy. They have attracted great attention due to their advantages of low cost, ease of synthesis, light weight, mechanical flexibility, and roll-to-roll processability. In the past decades, owing to the development of the materials, device optimization and the understanding of the working mechanism, the power conversion efficiency (PCE) has been boosted to ~19%. However, the efficiency of the OSCs is still not comparable to the conventional inorganic solar cells and emerging perovskite solar cells due to the large open-circuit voltage loss (V_loss). In addition, it is also important to obtain efficient charge generation while reducing the V_loss. Thus, understanding the loss mechanisms in the OSCs is significant for achieving further improvement.

In this thesis, a novel small-molecule donor named ZR1 was used to fabricate all-small-molecule OSCs (SM-OSCs), which shows efficient charge separation and transport with the optimized hierarchical morphologies, obtaining a breakthrough efficiency of 13.34% with a low V_loss (0.54 eV) in SM-OSCs. In this system, the energy offsets between the donor and acceptor (ΔHOMO or ΔLUMO) play an important role in the open-circuit voltage (V_OC) of the OSCs. According to the optoelectronic reciprocity introduced in this thesis, the sub-gap absorption and emission by charge transfer (CT) states lead to large radiative and non-radiative recombination losses. The results show that the decreased HOMO offsets between donor and acceptor can effectively reduce both radiative and non-radiative recombination losses from the CT states, resulting in a suppressed V_loss.

In addition to the SM-OSCs, we also study the V_loss and charge generation in the all-polymer OSCs (all- PSCs). A series of polymer acceptors were designed and applied in all-PSCs. In this work, all devices with negligible LUMO offsets show high V_OCs of 1.02-1.15 V and good short-circuit currents (JSCs) of 8.87-15.16 mA cm⁻² as well as small V_losss. This study reveals that the small V_loss and the effective charge generation can also be realized simultaneously in all-PSCs with small energy offsets.

Next, we found that introducing a third component can also reduce V_loss. In this work, we start with the fundamental photophysical processes which determine the V_OCs of the devices and provide a universal approach framework well explaining the V_OC of ternary OSCs (TOSCs) in different situations. By combining experimental investigations with theoretical simulations, we highlight the significant influence of the thermal population arising from the guest component-related CT states and local excited (LE)states on the non-radiative recombination losses in TOSCs. Firmly based on our new understanding, we provide design rules for enhancing the V_OC in TOSCs: 1) high emission yield for the guest binary system; close charge-transfer energies between two binary systems; 2) high miscibility of the guest component with the low-optical-gap component in the host binary blends.

In the all-PSCs work we did before, we find the small V_loss and the effective charge generation can be achieved simultaneously with small energy offsets, which can be also observed in other non-fullerene based OSCs. It was found that some of non-fullerene acceptors based OSCs can realize an efficient charge generation and a suppressed charge recombination process with small energy offsets (< 0.3 eV) between the donor and the acceptor, leading to a low V_loss, a high JSC, and a high fill factor (FF) simultaneously. Here, we investigate a series of OSCs blends with different HOMO offsets between donor and in a large range of ~ 0 to 0.50 eV. Along with decreasing HOMO offsets, the blends show reduced V_losss. For the JSC and the FF, we observe a maximum value at an optimal energetic offset around 0.2-0.3 eV and the optimal energetic offset appears at different values for different non-fullerene acceptors. Through the analysis of the ultrafast transient absorption, we find inefficient charge generation when the HOMO offset is close to zero, which attributed to the back transfer of a hole from the donor to the acceptor. The affected charge generation at the small HOMO offsets is probably the main reason for the deceased JSC and FF. This study demonstrates the existence of optimal energy offsets for achieving high-performance OSCs.