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Random terpolymerization is an effective approach to achieving highly efficient and outdoor-stable terpolymer photovoltaics. However, the working principle behind this remains unclear. Herein, we report spectroscopic, morphological, and computational results and conclude the previous work on terpolymer research to unveil their structure–property relations and elucidate key rules for high-efficiency and outdoor-stable terpolymer photovoltaics. More specifically, introducing a strong electron-deficient or electron-rich third moiety is suggested to enable broadened absorption with minimized non-radiative voltage losses. Besides, the third component should manipulate the D/A miscibility towards a thermodynamically more stable morphology. However, the content of the third component should be small to maintain molecular orientation and exciton diffusion length in conjunction with optimized phase-separation and crystallinity, in turn reducing bimolecular carrier recombination. Obeying these rules, terpolymer solar cells based on the parent donors D18 and PM6 with enhanced power conversion efficiency (PCE) and excellent outdoor stability are demonstrated. Our findings provide a rationale for explaining and achieving high-performance and outdoor-stable terpolymer photovoltaics, paving the path to commercialization.

Accelerating the shift towards renewable materials and sustainable processes for printed organic electronic devices is crucial for a green circular economy. Currently, the fabrication of organic devices with competitive performances is linked to toxic petrochemical-based solvents with considerable carbon emissions. Here we show that terpene solvents obtained from renewable feedstocks can replace non-renewable environmentally hazardous solvent counterparts in the production of highly efficient organic photovoltaics (OPVs) light-emitting diodes (OLEDs) and field-effect transistors (OFETs) with on-par performances. Using a Hansen solubility ink formulation framework, we identify various terpene solvent systems and investigate effective film formation and drying mechanisms required for optimal charge transport. This approach is universal for state-of-the-art materials in OPVs, OLEDs and OFETs. We created an interactive library for green solvent selections and made it publicly available through the OMEGALab website. As potential carbon-negative solvents, terpenes open a unique and universal approach towards efficient, large-area and stable organic electronic devices.

If perovskite solar cells (PSCs) with high power conversion efficiencies (PCEs) are to be commercialized, they must achieve long-term stability, which is usually assessed with accelerated degradation tests. One of the persistent obstacles for PSCs has been successfully passing the damp-heat test (85°C and 85% relative humidity), which is the standard for verifying the stability of commercial photovoltaic (PV) modules. We fabricated damp heat–stable PSCs by tailoring the dimensional fragments of two-dimensional perovskite layers formed at room temperature with oleylammonium iodide molecules; these layers passivate the perovskite surface at the electron-selective contact. The resulting inverted PSCs deliver a 24.3% PCE and retain >95% of their initial value after >1000 hours at damp-heat test conditions, thereby meeting one of the critical industrial stability standards for PV modules.

High-efficiency perovskite-based solar cells comprise sophisticated stacks of materials which, however, often feature different thermal expansion coefficients and are only weakly bonded at their interfaces. This may raise concerns over delamination in such devices, jeopardizing their long-term stability and commercial viability. Here, we investigate the root causes of catastrophic top-contact delamination we observed in state-of-the-art p-i-n perovskite/silicon tandem solar cells. By combining macroscopic and microscopic analyses, we identify the interface between the fullerene electron transport layer and the tin oxide buffer layer at the origin of such delamination. Specifically, we find that the perovskite morphology and its roughness play a significant role in the microscopic adhesion of the top layers, as well as the film processing conditions, particularly the deposition temperature and the sputtering power. Our findings mandate the search for new interfacial linking strategies to enable mechanically strong perovskite-based solar cells, as required for commercialization.

Summary Stacking perovskite solar cells onto crystalline silicon bottom cells in a monolithic tandem configuration enables power-conversion efficiencies (PCEs) well above those of their single-junction counterparts. However, state-of-the-art wide-band-gap perovskite films suffer from phase stability issues. Here, we show how carbazole as an additive to the perovskite precursor solution can not only reduce nonradiative recombination losses but, perhaps more importantly, also can suppress phase segregation under exposure to moisture and light illumination. This enables a stabilized PCE of 28.6% (independently certified at 28.2%) for a monolithic perovskite/silicon tandem solar cell over ∼1 cm2 and 27.1% over 3.8 cm2, built from a textured silicon heterojunction solar cell. The modified tandem devices retain ∼93% of their performance over 43 days in a hot and humid outdoor environment of almost 100% relative humidity over 250 h under continuous 1-sun illumination and about 87% during a 85/85 damp-heat test for 500 h, demonstrating the improved phase stability.

Advanced functional materials 33(4), 2205557 (2023). doi:10.1002/adfm.202205557, Textured silicon wafers used in silicon solar cell manufacturing offer superior light trapping, which is a critical enabler for high-performance photovoltaics. A similar optical benefit can be obtained in monolithic perovskite/silicon tandem solar cells, enhancing the current output of the silicon bottom cell. Yet, such complex silicon surfaces may affect the structural and optoelectronic properties of the overlying perovskite films. Here, through extensive characterization based on optical and microstructural spectroscopy, it is found that the main effect of such substrate morphology lies in an altering of the photoluminescence response of the perovskite, which is associated with thickness variations of the perovskite, rather than lattice strain or compositional changes. With this understanding, the design of high-performance perovskite/silicon tandems is rationalized, yielding certified power conversion efficiencies of >28%., Published by Wiley-VCH, Weinheim

Perovskite/silicon tandem solar cells are emerging as a high-efficiency and prospectively cost-effective solar technology with great promise for deployment at the utility scale. However, despite the remarkable performance progress reported lately, assuring sufficient device stability-particularly of the perovskite top cell-remains a challenge on the path to practical impact. In this work, we analyze the outdoor performance of encapsulated bifacial perovskite/silicon tandems, by carrying out field-testing in Saudi Arabia. Over a six month experiment, we find that the open circuit voltage retains its initial value, whereas the fill factor degrades, which is found to have two causes. A first degradation mechanism is linked with ion migration in the perovskite and is largely reversible overnight, though it does induce hysteretic behavior over time. A second, irreversible, mechanism is caused by corrosion of the silver metal top contact with the formation of silver iodide. These findings provide directions for the design of new and more stable perovskite/silicon tandems

The performance of perovskite solar cells with inverted polarity (p-i-n) is still limited by recombination at their electron extraction interface, which also lowers the power conversion efficiency (PCE) of p-i-n perovskite-silicon tandem solar cells. A MgF x interlayer with thickness of ~1 nanometer at the perovskite/C 60 interface favorably adjusts the surface energy of the perovskite layer through thermal evaporation, which facilitates efficient electron extraction and displaces C 60 from the perovskite surface to mitigate nonradiative recombination. These effects enable a champion open-circuit voltage of 1.92 volts, an improved fill factor of 80.7%, and an independently certified stabilized PCE of 29.3% for a monolithic perovskite-silicon tandem solar cell ~1 square centimeter in area. The tandem retained ~95% of its initial performance after damp-heat testing (85°C at 85% relative humidity) for >1000 hours.

Solution-processed organic photodetectors (OPDs) sensitive to infrared (IR) light have the potential to be used in various technologies from health monitoring to communication. These detectors require low bandgap materials absorbing photons beyond 750 nm with high responsivity. In this work, an ultra-low bandgap non-fullerene acceptor (NFA) that absorbs light until 1020 nm is developed. Used in a bulk heterojunction (BHJ)-based device, the photodetector has a maximum responsivity of 0.50 A W−1 at 890 nm without bias voltage comparable with silicon-based detectors. Due to high and balanced mobilities of 10−4 cm2 V−1 s−1, the device has a fast speed of response to IR (i.e. rise and decay time less than 4 μs) and minor damping of 1 dB in the IR communication range (38–50 kHz). The organic photodetector transcripts with accuracy the message emitted around 910 nm from a commercial remote control, thus demonstrating the potential of organic electronics for infrared communication.

Solution-processable small molecules (SMs) that can serve as donors in bulk-heterojunction (BHJ) solar cells are practical alternatives to their polymer counterparts. However, SM–fullerene blends c...

Translating the high power conversion efficiencies of single-junction perovskite solar cells in their classic, non-inverted (n-i-p) architecture to efficient monolithic n-i-p perovskite/silicon tandem solar cells with high current densities has been a persistent challenge due to the lack of low-temperature processable, chemically-insoluble contact materials with appropriate polarity and sufficient optical transparency. To address this, we developed sputtered amorphous niobium oxide (a-NbOx) with ligand-bridged C-60 as an efficient electron-selective contact, deposited on the textured-silicon bottom cell. For the sunward, hole-selective contact we implemented a stack of molecularly doped broadband transparent evaporated 2,2 ',7,7 '-tetra(N,N-di-p-tolyl)amino-9,9-spirobifluorene (spiro-TTB) and atomic layer deposited vanadium oxide, which further enhances the device quantum efficiency. Combining these contact materials with two-dimensional perovskite passivation on the micrometer-thick solution-processed perovskite top cell yields 27% efficient monolithic n-i-p perovskite/silicon tandem solar cells, which represents one of the highest power conversion efficiencies reported on pyramidal textured crystalline silicon bottom cells, and the highest with this polarity. The authors would like to thanks to Nini Wei for the TEM images; funding: the research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST) under award no. OSR-CARF/CCF-3079 and award no. IED OSR-2019-4208.

It is well established that for organic photodetectors (OPDs) to compete with their inorganic counterparts, low dark currents at reverse bias must be achieved. Here, two rhodanine-terminated nonfullerene acceptors O-FBR and O-IDTBR are shown to deliver low dark currents at -2 V of 0.17 and 0.84 nA cm-2, respectively, when combined with the synthetically scalable polymer PTQ10 in OPD. These low dark currents contribute to the excellent sensitivity to low light of the detectors, reaching values of 0.57 μW cm-2 for PTQ10:O-FBR-based OPD and 2.12 μW cm-2 for PTQ10:O-IDTBR-based OPD. In both cases, this sensitivity exceeds that of a commercially available silicon photodiode. The responsivity of the PTQ10:O-FBR-based OPD of 0.34 AW-1 under a reverse bias of -2 V also exceeds that of a silicon photodiode. Meanwhile, the responsivity of the PTQ10:O-IDTBR of 0.03 AW-1 is limited by the energetic offset of the blend. The OPDs deliver high specific detectivities of 9.6 × 1012 Jones and 3.3 × 1011 Jones for O-FBR- and O-IDTBR-based blends, respectively. Both active layers are blade-coated in air, making them suitable for high-throughput methods. Finally, all three of the materials can be synthesized at low cost and on a large scale, making these blends good candidates for commercial OPD applications.

Three symmetrically difluorinated organic semiconductors (namely D5T2F-P, D5T2F-S, and D5T2F-T) containing rhodanine-flanked pentathiophene structures are synthesized and used as donors in all-small-molecule organic solar cells (ASM-OSCs) prepared with the small-molecule acceptor 2,2′-((2Z,2′Z)-((4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b′]dithiophene-2,7-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (IDIC-4F). The different substitutional positions of fluorine atoms (–F) in the conjugated backbone of the donor molecule lead to various material and photovoltaic properties being exhibited. Among the three isomers, the centrally fluorinated D5T2F-P exhibits a redshifted absorption spectrum, downshifted highest occupied molecular orbital (HOMO) energy level, and improved miscibility with IDIC-4F in the blend films, all of which result in superior device performance. The power conversion efficiency (PCE) of the ASM-OSCs based on D5T2F-P:IDIC-4F reaches an impressive value of 9.36% with an open-circuit voltage (VOC) value of 0.86 V and a short-circuit current density (JSC) value of 16.94 mA cm−2, whereas those of D5T2F-S (6.11%) and D5T2F-T (5.42%) are much lower. In comparison, an ASM-OSC based on the nonfluorinated analogue DRCN5T fabricated under the same conditions exhibits poorer performance (8.03% with IDIC-4F), revealing 16% enhancement in the PCE achieved through backbone fluorination. The PCE of 9.36% may be one of the highest efficiencies of oligothiophene-based ASM-OSCs reported in the literature to date.

End-group-directed molecular self-assembly can be an effective strategy in the design of “organic electronics” amenable to specific morphologies and charge transport patterns for device applications. In this study, we report on the design, self-ordering, and transistor characteristics of an analogous set of pyrene-functionalized diketopyrrolopyrroles (DPP; namely, SM1–3) obtained by “successive incorporation” of DPP motifs. The well-defined pyrene-substituted DPP analogues are systematically examined in correlation of (i) the number of incorporated DPP motifs in the π-extended main-chain and (ii) the solution-processing conditions employed for the thin film formation. Solvent vapor enhanced drop-casting (SVED) from chloroform (CHCl3) and tetrahydrofuran (THF) are found to promote very distinct, long-range morphologies of SM1–3. During THF-mediated SVED, the growth of a one-dimensional fiber of SM1–3 originates from the formation of initial aggregates in THF. In particular, extending the π-conjugation of t...

Small-molecule (SM) donors that can be solution-processed with fullerene acceptors (e.g., PC61/71BM), or their “nonfullerene” counterparts, are proving particularly promising for the realization of high-efficiency bulk-heterojunction (BHJ) solar cells. In several recent studies, solvent vapor annealing (SVA) protocols have been found to yield significant BHJ device efficiency improvements via structural changes in the active layer morphologies. However, the mechanisms by which active layer morphologies evolve when subjected to SVA treatments, and the structural factors impacting charge generation, carrier transport, recombination, and extraction in BHJ solar cells with SM donors and fullerene acceptors, remain important aspects to be elucidated. In this report, we show that—in BHJ solar cells with SM donors and fullerene acceptors—selective crystallization promoted by SVA mediates the development of optimized morphologies across the active layers, setting domain sizes and boundaries. Examining BHJ solar c...

Tin-doped indium oxide (ITO) transparent conducting electrodes are widely used across the display industry, and are currently the cornerstone of photovoltaic device developments, taking a substantial share in the manufacturing cost of large-area modules. However, cost and supply considerations are set to limit the extensive use of indium for optoelectronic device applications and, in turn, alternative transparent conducting oxide (TCO) materials are required. In this report, we show that aluminum-doped zinc oxide (AZO) thin films grown by atomic layer deposition (ALD) are sufficiently conductive and transparent to outperform ITO as the cathode in inverted polymer solar cells. Reference polymer solar cells made with atomic-layer-deposited AZO cathodes, PCE10 as the polymer donor and PC71BM as the fullerene acceptor (model systems), reach power conversion efficiencies of ca. 10% (compared to ca. 9% with ITO-coated glass), without compromising other figures of merit. These ALD-grown AZO electrodes are promising for a wide range of optoelectronic device applications relying on TCOs.

We report on a set of two analogous, F-substituted oligothiophene derivatives (D5T6F-M and D7T8F-M), in which systematic fluorination at the thienyl moieties is shown to induce a sufficient increase in electron affinity (EA; i.e. suppressed LUMO level) and in ionization potential (IP; i.e. deeper HOMO) to (i) impart the molecules with electron-accepting and -transporting characteristics, and (ii) yield high open-circuit voltages >1 V in BHJ solar cells when combined with a low-bandgap polymer donor (PCE10) commonly used with fullerenes. The nonfullerene BHJ devices with the SM acceptor D5T6F-M achieve power conversion efficiencies (PCEs) of up to ca. 4.5% (vs. ca. 2% for D7T8F-M-based devices). Our study shows that –F substitutions in SM systems – otherwise used as donors – is an effective approach in the design of nonfullerene acceptors for efficient BHJ solar cells with polymer donors.

International audience; Polymer acceptors are a class of “non‐fullerene” electron‐transporting materials that can replace [6,6]‐phenyl C61/71 butyric acid (PC61/71BM) in bulk‐heterojunction (BHJ) solar cells. In this contribution is reported the use of N‐acyl‐substituted isoindigo (IID) motifs (IID(CO)) as electron‐deficient units in the design of polymer acceptors for “all‐polymer” BHJ solar cells. While IID motifs are commonly used in the design of polymer donors for efficient BHJ solar cells with the fullerene PC61/71BM acceptors, here it is shown that IID(CO) building units used in conjunction with suitable co‐monomers represent a practical avenue for polymer acceptors with electron affinity values comparable to that of PC61/71BM (i.e., 4.2 eV).

Well-defined small molecule (SM) donors can be used as alternatives to π-conjugated polymers in bulk-heterojunction (BHJ) solar cells with fullerene acceptors (e.g., PC61/71BM). Taking advantage of their synthetic tunability, combinations of various donor and acceptor motifs can lead to a wide range of optical, electronic, and self-assembling properties that, in turn, may impact material performance in BHJ solar cells. In this report, it is shown that changing the sequence of donor and acceptor units along the π-extended backbone of benzo[1,2-b:4,5-b′]dithiophene–6,7-difluoroquinoxaline SM donors critically impacts (i) molecular packing, (ii) propensity to order and preferential aggregate orientations in thin-films, and (iii) charge transport in BHJ solar cells. In these systems (SM1-3), it is found that 6,7-difluoroquinoxaline ([2F]Q) motifs directly appended to the central benzo[1,2-b:4,5-b′]dithiophene (BDT) unit yield a lower-bandgap analogue (SM1) with favorable molecular packing and aggregation patterns in thin films, and optimized BHJ solar cell efficiencies of ≈6.6%. 1H-1H DQ-SQ NMR analyses indicate that SM1 and its counterpart with [2F]Q motifs substituted as end-group SM3 possess distinct self-assembly patterns, correlating with the significant charge transport and BHJ device efficiency differences observed for the two analogous SM donors (avg. 6.3% vs 2.0%, respectively).

Low-bandgap small molecule (SM) donors that can be solution-processed with fullerene acceptors (e.g., PC61/71BM) are proving to be particularly promising in bulk-heterojunction (BHJ) solar cells. Compared to their π-conjugated polymer counterparts, SM donors are well-defined (monodisperse) and more synthetically modular, with relatively wide ranges of bandgaps that can be achieved in stepwise couplings of various donor and acceptor motifs. However, the optimization of SM–fullerene morphologies and BHJ device efficiencies relies more specifically on the use of processing additives, postprocessing thermal, or solvent vapor annealing (SVA) approaches, and achieving adequate interpenetrating networks and structural order in BHJ thin films can be challenging. In this report, we examine the correlated effects of molecular structure and postprocessing SVA on the BHJ solar cell performance of a set of π-extended SM donors composed of dithieno[3,2-b:2′,3′-d]pyrrole (DTP) and 5,6-difluorobenzo[c][1,2,5]thiadiazole ...

Molecular acceptors are promising alternatives to fullerenes (e.g., PC61/71BM) in the fabrication of high-efficiency bulk-heterojunction (BHJ) solar cells. While solution-processed polymer–fullerene BHJ devices have recently met the 10% efficiency threshold, molecular acceptors have yet to prove comparably efficient with polymer donors. At this point in time, it is important to forge a better understanding of the design parameters that directly impact small-molecule (SM) acceptor performance in BHJ solar cells. In this report, we show that 2-(benzo[c][1,2,5]thiadiazol-4-ylmethylene)malononitrile (BM)-terminated SM acceptors can achieve efficiencies as high as 5.3% in BHJ solar cells with the polymer donor PCE10. Through systematic device optimization and characterization studies, we find that the nonfullerene analogues (FBM, CBM, and CDTBM) all perform comparably well, independent of the molecular structure and electronics of the π-bridge that links the two electron-deficient BM end groups. With estimated...

Efficiencies of organic photovoltaic (OPV) devices have been steadily climbing, but there is still a prominent gap in understanding the relationship between fabrication and performance. Side chain substitution is one processing parameter that can change OPV device efficiency considerably, primarily because of variations in morphology. In this work, we explain the morphological link between side chain selection and device performance in one polymer to aid in the development of design rules more broadly. We study the morphology of an OPV active layer using a PBDTTPD-backbone polymer with four different side chain configurations, which are shown to change device efficiency by up to 4 times. The optimal device has the smallest domain sizes, the highest degree of crystallinity, and the most face-on character. This is achieved with two branched 2-ethylhexyl (2EH) side chains placed symmetrically on the BDT unit and a linear octyl (C8) side chain on the TPD unit. Substituting either side chain (C14 on BDT and/or 2EH on TPD) makes the orientation less face-on, while the TPD side chain primarily affects domain size. For all side chains, the addition of fullerene increases polymer crystallization compared to the neat film, but the degree of mixing between polymer and fullerene varies with side chain. Interestingly, the optimal device has a negligible amount of mixed phase. The domain sizes present in the optimal system are remarkably unchanged with a changing fullerene ratio between 10 and 90%, hinting that the polymer preferentially self-assembles into 10-20 nm crystallites regardless of concentration. The formation of this crystallite may be the key factor inhibiting mixed phase.

It is established that the nanomorphology plays an important role in performance of bulk-heterojunction (BHJ) organic solar cells. From intense research in polymer-fullerene systems, some trends are becoming apparent. For example, small ~10 nm domains, high crystallinity, and low miscibility are typically measured in high-performance systems. However, the generality of these concepts for small-molecule (SM) BHJs is unclear. We present a comprehensive study of performance, charge generation and extraction dynamics, and nanomorphology in SM-fullerene BHJ devices to probe these critical structure-property relationships in this class of materials. In the systems investigated, small domains remain important for performance. However, devices composed of highly mixed domains with modest crystallinity outperform those consisting of pure/highly crystalline domains. Such a result points to an alternative ideal morphology for SM-based devices that involves a predominant mixed phase. This stems from SM aggregation in highly mixed domains that both maximize interface for charge generation and establish continuous pathways for efficient charge extraction. Such a morphological paradigm should be considered in future SM systems in pursuit of high-efficiency large-scale solar power production.

The interplay between nanomorphology and efficiency of polymer-fullerene bulk-heterojunction (BHJ) solar cells has been the subject of intense research, but the generality of these concepts for small-molecule (SM) BHJs remains unclear. Here, the relation between performance; charge generation, recombination, and extraction dynamics; and nanomorphology achievable with two SM donors benzo[1,2-b:4,5-b]dithiophene-pyrido[3,4-b]-pyrazine BDT(PPTh2)(2), namely SM1 and SM2, differing by their side-chains, are examined as a function of solution additive composition. The results show that the additive 1,8-diiodooctane acts as a plasticizer in the blends, increases domain size, and promotes ordering/crystallinity. Surprisingly, the system with high domain purity (SM1) exhibits both poor exciton harvesting and severe charge trapping, alleviated only slightly with increased crystallinity. In contrast, the system consisting of mixed domains and lower crystallinity (SM2) shows both excellent exciton harvesting and low charge recombination losses. Importantly, the onset of large, pure crystallites in the latter (SM2) system reduces efficiency, pointing to possible differences in the ideal morphologies for SM-based BHJ solar cells compared with polymer-fullerene devices. In polymer-based systems, tie chains between pure polymer crystals establish a continuous charge transport network, whereas SM-based active layers may in some cases require mixed domains that enable both aggregation and charge percolation to the electrodes.

We report on the synthesis, material properties, and bulk heterojunction (BHJ) solar cell characteristics of a set of π-conjugated small-molecule (SM) donors composed of benzo[1,2-b:4,5-b′]dithiophene (BDT) and pyrido[3,4-b]pyrazine (PP) units, examining the perspectives of alkyl-substituted PP acceptor motifs in SM designs. In these systems (SM1–4), both the type of side chains derived from the PP motifs and the presence of ring substituents on BDT critically impact (i) molecular packing, and (ii) thin-film morphologies and charge transport in BHJ solar cells. With the appropriate side-chain pattern, the ring-substituted analogue SM4 stands out, achieving efficiencies of ca. 6.5% with PC71BM, and fine-scale morphologies comparable to those obtained with some of the best-performing polymer donors in BHJ solar cells. 1H–1H DQ-SQ NMR analyses are used to examine the distinct self-assembly pattern of SM4, expected to factor into the development of the BHJ morphology.

International audience; A push–pull σ–C60 molecular dyad was synthesized via Huisgen-type click chemistry and used as photoactive material for single-component organic solar cells. Steady-state photoluminescence (PL) experiments of the dyad in solution show a significant quenching of the emission of the push–pull moiety. Spin-casting of a solution of the dyad results in homogeneous and smooth thin films, which exhibit complete PL quenching in line with ultrafast photoinduced electron-transfer in the solid state. Spectroelectrochemistry reveals the optical signatures of radical cations and radical anions. Evaluation of the charge carrier mobility by space-charge limited current measurements gives an electron-mobility of μe = 4.3 × 10–4 cm2 V–1 s–1, ca. 50 times higher than the hole-mobility. Single-component organic solar cells yield an open-circuit voltage Voc of 0.73 V and a short-circuit current density of 2.1 mA cm–2; however, a poor fill factor FF (29%) is obtained, resulting in low power conversion efficiency of only 0.4%. Combined transient absorption (TA) and time-delayed collection field (TDCF) experiments show mostly ultrafast photon-to-charge conversion and a small component of diffusion-limited exciton dissociation, revealing the presence of pure fullerene domains. Furthermore, a strong field dependence of charge generation is observed, governing the device fill factor, which is further reduced by a competition between extraction and fast recombination of separated charges.

This publication was based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. CRG_R2_13_BEAU_KAUST_1. The authors acknowledge concurrent support under Baseline Research Funding from KAUST. The authors thank KAUST ACL for technical support in the mass spectrometry analyses. V.S. acknowledges financial support from the NDSEG fellowship. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.

Achieving efficient bulk-heterojunction (BHJ) solar cells from blends of solution-processable small-molecule (SM) donors and acceptors is proved particularly challenging due to the complexity in obtaining a favorable donor–acceptor morphology. In this report, the BHJ device performance pattern of a set of analogous, well-defined SM donors—DR3TBDTT (DR3), SMPV1, and BTR—used in conjunction with the SM acceptor IDTTBM is examined. Examinations show that the nonfullerene “All-SM” BHJ solar cells made with DR3 and IDTTBM can achieve power conversion efficiencies (PCEs) of up to ≈4.5% (avg. 4.0%) when the solution-processing additive 1,8-diiodooctane (DIO, 0.8% v/v) is used in the blend solutions. The figures of merit of optimized DR3:IDTTBM solar cells contrast with those of “as-cast” BHJ devices from which only modest PCEs

Solution-processable small molecule (SM) donors are promising alternatives to their polymer counterparts in bulk-heterojunction (BHJ) solar cells. While SM donors with favorable spectral absorption, self-assembly patterns, optimum thin-film morphologies, and high carrier mobilities in optimized donor–acceptor blends are required to further BHJ device efficiencies, material structure governs each one of those attributes. As a result, the rational design of SM donors with gradually improved BHJ solar cell efficiencies must concurrently address: (i) bandgap tuning and optimization of spectral absorption (inherent to the SM main chain) and (ii) pendant-group substitution promoting structural order and mediating morphological effects. In this paper, the rational pendant-group substitution in benzo[1,2-b:4,5-b′]dithiophene–6,7-difluoroquinoxaline SMs is shown to be an effective approach to narrowing the optical gap (Eopt) of the SM donors (SM1 and SM2), without altering their propensity to order and form favorable thin-film BHJ morphologies with PC71BM. Systematic device examinations show that power conversion efficiencies >8% and open-circuit voltages (VOC) nearing 1 V can be achieved with the narrow-gap SM donor analog (SM2, Eopt = 1.6 eV) and that charge transport in optimized BHJ solar cells proceeds with minimal, nearly trap-free recombination. Detailed device simulations, light intensity dependence, and transient photocurrent analyses emphasize how carrier recombination impacts BHJ device performance upon optimization of active layer thickness and morphology.