Compositional engineering of interfacial charge transfer in van der Waals heterostructures of graphene and transition metal dichalcogenides.

Owing to their unique optical and electronic properties, vertical van der Waals heterostructures (vdWHs) have attracted considerable attention in optoelectronic applications, such as photodetection, light harvesting, and light-emitting diodes. To fully harness these properties, it is crucial to understand the interfacial charge transfer (CT) and recombination dynamics across vdWHs. However, the effects of interfacial energetics and defect states on interfacial CT and recombination processes in graphene-transition metal dichalcogenide (Gr-TMD) vdWHs remain debated. Here, we investigate the interfacial CT dynamics in Gr-TMD vdWHs with different chemical compositions (W, Mo, S, and Se) and tunable interfacial energetics. We demonstrate, using ultrafast terahertz spectroscopy, that while the photo-induced electron transfer direction is universal with graphene donating electrons to TMDs, its efficiency is chalcogen-dependent: the CT efficiency of S atom-based vdWHs is 3-5 times higher than that of Se-based vdWHs thanks to the lower Schottky barrier present in S-based vdWHs. In contrast, the electron back transfer process from TMD to Gr, which defines the charge separation time, is transition metal-dependent and dominated by the mid-gap defect level of TMDs: W transition metal-based vdWHs possess extremely long charge separation, well beyond 1 ns, which is significantly longer than Mo-based vdWHs with only 10 s of ps charge separation. This difference can be traced to the much deeper mid-gap defect reported in W-based TMDs compared to Mo-based ones, resulting in modified energetics for the back electron transfer from the trapped states to graphene. Our results shed light on the role of interfacial energetics and defects by tailoring chemical compositions of TMDs on the interfacial CT and recombination dynamics in Gr-TMD vdWHs, which is pivotal for optimizing optoelectronic devices, particularly in the field of photodetection.

Charge photogeneration dynamics in non-fullerene polymer solar cells with fluorinated and non-fluorinated acceptors.

In this work, charge photogeneration and recombination processes of PM6:IDIC-4F and PM6:IDIC blend films were investigated by the steady-state and time-resolved spectroscopies, as well as the time-dependent density functional theory calculations. The peaks in absorption and photoluminescence (PL) spectra of IDIC and IDIC-4F solutions were assigned by combining the experiment and the simulation of UV-vis absorption and PL spectra. For neat acceptor films, the exciton diffusion length of neat IDIC and IDIC-4F films was estimated as ∼28.9 and ∼19.9 nm, respectively. For PM6-based blend films, we find that the fluorine substitution engineering on the IDIC acceptor material can increase the phase separate size of acceptor material in blend films, resulting in the reduction of dissociation efficiencies of acceptor excitons. In addition, we find that the charge recombination in PM6:IDIC-4F is dominated by bimolecular recombination, in comparison to geminate type carrier recombination in PM6:IDIC blend films. In addition, we find that thermal annealing treatment has a weak influence on carrier recombination but slightly reduces the exciton dissociation efficiency of acceptor in PM6:IDIC blend films, leading to a slightly reduced power conversion efficiency of PM6:IDIC solar cells. These results may shed light on the design of high-performance semiconductor molecules for application in solar cells.

An Insight into the Excitation States of Small Molecular Semiconductor Y6.

Y6 is a new type of non-fullerene acceptor, which has led to power conversion efficiencies of single-junction polymer solar cells over 17% when combined with a careful choice of polymeric donors. However, the excited state characteristics of Y6, which is closely correlated with its opto-electronic applications, are not clear yet. In this work, we studied the excited state properties of the Y6 solution and Y6 film, by using steady-state and time-resolved spectroscopies as well as time-dependent density functional theory (TD-DFT) calculations. UV-Vis absorption and fluorescence simulation, natural transition orbitals (NTOs) and hole-electron distribution analysis of Y6 solution were performed for understanding the excitation properties of Y6 by using TD-DFT calculations. The lifetimes of the lowest singlet excited state in Y6 solution and film were estimated to be 0.98 and 0.8 ns, respectively. Combining the exciton lifetime and photoluminescence (PL) quantum yield, the intrinsic radiative decay lifetimes of Y6 in the solution and film were estimated, which were 1.3 and 10.5 ns for the Y6 solution and film, respectively. Long exciton lifetime (~0.8 ns) and intrinsic radiative decay lifetime (~10.5 ns) of Y6 film enable Y6 to be a good acceptor material for the application of polymer solar cells.

Photoinduced Polaron Formation in a Polymerized Electron-Acceptor Semiconductor.

Polymerized small molecular acceptor (PSMA) based all-polymer solar cells (all-PSC) have achieved power conversion efficiencies (PCE) over 16%, and the PSMA is considered to hold great promise for further improving the performance of all-PSC. Yet, in comparison with that of the polymer donor, the photophysics of a polymerized acceptor remains poorly understood. Herein, the excited state dynamics in a polymerized acceptor PZT810 was comprehensively investigated under various pump intensities and photon energies. The excess excitation energy was found to play a key role in excitons dissociation into free polarons for neat PSMA films, while free polarons cannot be generated from the polaron pairs in neat acceptor films. This work reveals an in-depth understanding of relaxation dynamics for PSMAs and that the underlying photophysical origin of PSMA can be mediated by excitation energies and intensities. These results would benefit the realization of the working mechanism for all-PSC and the designing of new PSMAs.

Ground- and excited-state characteristics in photovoltaic polymer N2200.

As a classical polymer acceptor material, N2200 has received extensive attention and research in the field of polymer solar cells (PSCs). However, the intrinsic properties of ground- and excited-states in N2200, which are critical for the application of N2200 in PSCs, remain poorly understood. In this work, the ground- and excited-state properties of N2200 solution and film were studied by steady-state and time-resolved spectroscopies as well as time-dependent density functional theory (TD-DFT) calculations. The transition mechanism of absorption peaks of N2200 was evaluated through the natural transition orbitals (NTOs) and hole-electron population analysis by TD-DFT. Time-resolved photoluminescence (TRPL) study shows that the lifetimes of singlet excitons in N2200 chlorobenzene solution and film are ∼90 ps and ∼60 ps, respectively. Considering the absolute quantum yield of N2200 film, we deduce that the intrinsic lifetime of singlet exciton can be as long as ∼20 ns. By comparing the TRPL and transient absorption (TA) kinetics, we find that the decay of singlet excitons in N2200 solution is dominated by a fast non-radiative decay process, and the component induced by intersystem crossing is less than 5%. Besides that, the annihilation radius, annihilation rate and diffusion length of singlet excitons in N2200 film were evaluated as 3.6 nm, 2.5 × 10-9 cm3 s-1 and 4.5 nm, respectively. Our work provides comprehensive information on the excited states of N2200, which is helpful for the application of N2200 in all-PSCs.

Synergistic Engineering of Substituents and Backbones on Donor Polymers: Toward Terpolymer Design of High-Performance Polymer Solar Cells.

Design of terpolymers via copolymerization has emerged as a potential strategy for expanding the family of high-performing donor polymers and boosting the photovoltaic performance of non-fullerene polymer solar cells (PSCs). Herein, double-ester-substituted thiophenes and thienothiophenes are incorporated as third building blocks into the donor polymer PBDB-TF, developing two groups of terpolymers with donor-acceptor 1-donor-acceptor 2 (D-A1-D-A2)-type backbones. An optimum 10% concentration of double-ester-substituted thiophene units in PBDB-TF-T10 downshifts the molecular energy and increases the dielectric constant, and delivers proper miscibility and nanostructure in blends with the high-performing acceptor Y6. These characteristics are designed to synergistically enhance the photovoltage, photocurrent, and efficiency of PSCs. The resulting power conversion efficiency (PCE) of 16.4% surpasses the conventional PBDB-TF/Y6 PSCs, and it is among the best-performing PSCs based on PBDB-TF-derived terpolymers. Gratifyingly, PBDB-TF-T10 does not show significant batch-to-batch variation and it retains high PCEs above 16% in a broad range of molecular weights. This work introduces a facile strategy to easily synthesize terpolymers in combination with Y6 for the attainment of high-performing and reproducible non-fullerene PSCs.