Real-Time Probing and Unraveling the Morphology Formation of Blade-Coated Ternary Nonfullerene Organic Photovoltaics with In Situ X-Ray Scattering

Characterizing the bulk heterojunction (BHJ) morphology of the active layer is essential for optimizing blade-coated organic solar cells (OSCs). Here, the morphology evolution of a highly efficient ternary polymer:nonfullerene blend PM6:N3:N2200 under different blade coating conditions is probed in real-time by in situ synchrotron X-ray scattering and in situ ultraviolet-visible (UV-vis) spectroscopy. Besides, the morphology of blade-coated blend films at different conditions is detailed by ex situ X-ray scattering and microscopic imaging. The ternary blend film exhibited optimized morphology, such as superior molecular stacking structure and appropriate phase separation structure, and boosted photovoltaic performance of the binary blend, as adding a second polymer component to the host polymer:nonfullerene system can balance nucleation and crystallization of polymers and small molecules, facilitating molecular rearrangement to perfect crystallization. Both binary and ternary blends obtained optimized morphology and photovoltaic properties at medium coating speed, mainly attributed to the movement of the polymer and small molecules at the long crystallization and aggregation stage. These findings help understand morphology formation under film drying and provide guidance for optimizing the morphology in blade-coated OSCs.     

Post‐Deposition Activation of Latent Hydrogen‐Bonding: A New Paradigm for Enhancing the Performances of Bulk Heterojunction Solar Cells

Small conjugated molecules (SM) are gaining momentum as an alternative to semiconducting polymers for the production of solution‐processed bulk heterojunction (BHJ) solar cells. The major issue with SM‐BHJs is the low carrier mobility due to the scarce control on the phase‐segregation process and consequent lack of preferential percolative pathways for electrons and holes to the extraction electrodes. Here, a new paradigm for fine tuning the phase‐segregation in SM‐BHJs, based on the post‐deposition exploitation of latent hydrogen bonding in binary mixtures of PCBM with suitably functionalized electron donor molecules, is demonstrated. The strategy consist in the chemical protection of the H‐bond forming sites of the donor species with a thermo‐labile functionality whose controlled thermal cleavage leads to the formation of stable, crystalline, phase‐separated molecular aggregates. This approach allows the fine tuning of the nanoscale film connectivity and thereby to simultaneously optimize the generation of geminate carriers at the donor–acceptor interfaces and the extraction of free charges via ordered phase‐separated domains. As a result, the PV efficiency undergoes an over twenty‐fold increase with respect to control devices. This strategy, demonstrated here with mixtures of diketopyrrolopyrrole derivatives with PCBM can be extended to other molecular systems for achieving highly efficient SM‐BHJ solar cells.     

Effects of Thermal Annealing Upon the Morphology of Polymer–Fullerene Blends

Grazing incidence X‐ray scattering (GIXS) is used to characterize the morphology of poly(3‐hexylthiophene) (P3HT)–phenyl‐C61‐butyric acid methyl ester (PCBM) thin film bulk heterojunction (BHJ) blends as a function of thermal annealing temperature, from room temperature to 220 °C. A custom‐built heating chamber for in situ GIXS studies allows for the morphological characterization of thin films at elevated temperatures. Films annealed with a thermal gradient allow for the rapid investigation of the morphology over a range of temperatures that corroborate the results of the in situ experiments. Using these techniques the following are observed: the melting points of each component; an increase in the P3HT coherence length with annealing below the P3HT melting temperature; the formation of well‐oriented P3HT crystallites with the (100) plane parallel to the substrate, when cooled from the melt; and the cold crystallization of PCBM associated with the PCBM glass transition temperature. The incorporation of these materials into BHJ blends affects the nature of these transitions as a function of blend ratio. These results provide a deeper understanding of the physics of how thermal annealing affects the morphology of polymer–fullerene BHJ blends and provides tools to manipulate the blend morphology in order to develop high‐performance organic solar cell devices.     

In‐Plane Alignment in Organic Solar Cells to Probe the Morphological Dependence of Charge Recombination

Bulk heterojunction (BHJ) organic solar cells are fabricated with the polymer semiconductor aligned in the plane of the film to probe charge recombination losses associated with aggregates characterized by varying degrees of local order. 100% uniaxial strain is applied on ductile poly(3‐hexylthiophene):phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM) BHJ films and characterize the resulting morphology with ultraviolet‐visible absorption spectroscopy and grazing incidence X‐ray diffraction. It is found that the strained films result in strong alignment of the highly ordered polymer aggregates. Polymer aggregates with lower order and amorphous regions also align but with a much broader orientation distribution. The solar cells are then tested under linearly polarized light where the light is selectively absorbed by the appropriately oriented polymer, while maintaining a common local environment for the sweep out of photogenerated charge carriers. Results show that charge collection losses associated with a disordered BHJ film are circumvented, and the internal quantum efficiency is independent of P3HT local aggregate order near the heterojunction interface. Uniquely, this experimental approach allows for selective excitation of distinct morphological features of a conjugated polymer within a single BHJ film, providing insight into the morphological origin of recombination losses.     

Ternary mixing: A simple method to tailor the morphology of organic solar cells

We present a detailed study of the effects of ternary mixing on blend morphology, charge carrier mobility and organic solar cell performance. We investigate ternaries consisting of regio random poly(3-hexylthiophene) (P3HT), regio regular P3HT and soluble fullerene derivative, PCBM. By means of absorption, photoluminescence, atomic force microscopy and X-ray diffraction, we demonstrate that the structure of ternary films consists of crystallites of regular P3HT embedded into a random polymer matrix acting as a soft scaffolding where PCBM can only form nanoscale aggregates but cannot grow the detrimental micron-sized structures often observed in the conventional regular P3HT:PCBM case upon annealing. The ternary films exhibit higher degree of crystallinity than the conventional blends, but with smaller crystallite sizes. Moreover, we show that the addition of the random polymer chains does not prevent good charge carrier transport for regio random P3HT concentrations up to 50% of the total polymer content. Finally, we prove that solar cells based on the ternary systems have a similar short circuit current than the conventional binary, but improved open circuit current (by 100 mV), which leads to an overall enhancement of power conversion efficiency.     

Nanoscale Morphology of Conjugated Polymer/Fullerene‐Based Bulk‐ Heterojunction Solar Cells

The relation between the nanoscale morphology and associated device properties in conjugated polymer/fullerene bulk‐heterojunction “plastic solar cells” is investigated. We perform complementary measurements on solid‐state blends of poly[2‐methoxy‐5‐(3,7‐dimethyloctyloxy)]‐1,4‐phenylenevinylene (MDMO‐PPV) and the soluble fullerene C₆₀ derivative 1‐(3‐methoxycarbonyl) propyl‐1‐phenyl [6,6]C₆₁ (PCBM), spin‐cast from either toluene or chlorobenzene solutions. The characterization of the nanomorphology is carried out via scanning electron microscopy (SEM) and atomic force microscopy (AFM), while solar‐cell devices were characterized by means of current–voltage (I–V) and spectral photocurrent measurements. In addition, the morphology is manipulated via annealing, to increase the extent of phase separation in the thin‐film blends and to identify the distribution of materials. Photoluminescence measurements confirm the demixing of the materials under thermal treatment. Furthermore the photoluminescence of PCBM clusters with sizes of up to a few hundred nanometers indicates a photocurrent loss in films of the coarser phase‐separated blends cast from toluene. For toluene‐cast films the scale of phase separation depends strongly on the ratio of MDMO‐PPV to PCBM, as well as on the total concentration of the casting solution. Finally we observe small beads of 20–30 nm diameter, attributed to MDMO‐PPV, in blend films cast from both toluene and chlorobenzene.     

Three‐Dimensional Bulk Heterojunction Morphology for Achieving High Internal Quantum Efficiency in Polymer Solar Cells

Here, an investigation of three‐dimensional (3D) morphologies for bulk heterojunction (BHJ) films based on regioregular poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) is reported. Based on the results, it is demonstrated that optimized post‐treatment, such as solvent annealing, forces the PCBM molecules to migrate or diffuse toward the top surface of the BHJ composite films, which induces a new vertical component distribution favorable for enhancing the internal quantum efficiency (η_IQE ) of the devices. To investigate the 3D BHJ morphology, novel time‐of‐flight secondary‐ion mass spectroscopy studies are employed along with conventional methods, such as UV‐vis absorption, X‐ray diffraction, and high‐resolution transmission electron microscopy studies. The η_IQE of the devices are also compared after solvent annealing for different times, which clearly shows the effect of the vertical component distribution on the performance of BHJ polymer solar cells. In addition, the fabrication of high‐performance P3HT:PCBM solar cells using the optimized solvent‐annealing method is reported, and these cells show a mean power‐conversion efficiency of 4.12% under AM 1.5G illumination conditions at an intensity of 100 mW cm^?2.     

Understanding Local and Macroscopic Electron Mobilities in the Fullerene Network of Conjugated Polymer‐based Solar Cells: Time‐Resolved Microwave Conductivity and Theory

The efficiency of bulk heterojunction (BHJ) organic photovoltaics is sensitive to the morphology of the fullerene network that transports electrons through the device. This sensitivity makes it difficult to distinguish the contrasting roles of local electron mobility (how easily electrons can transfer between neighboring fullerene molecules) and macroscopic electron mobility (how well‐connected is the fullerene network on device length scales) in solar cell performance. In this work, a combination of density functional theory (DFT) calculations, flash‐photolysis time‐resolved microwave conductivity (TRMC) experiments, and space‐charge‐limit current (SCLC) mobility estimates are used to examine the roles of local and macroscopic electron mobility in conjugated polymer/fullerene BHJ photovoltaics. The local mobility of different pentaaryl fullerene derivatives (so‐called ‘shuttlecock’ molecules) is similar, so that differences in solar cell efficiency and SCLC mobilities result directly from the different propensities of these molecules to self‐assemble on macroscopic length scales. These experiments and calculations also demonstrate that the local mobility of phenyl‐C₆₀ butyl methyl ester (PCBM) is an order of magnitude higher than that of other fullerene derivatives, explaining why PCBM has been the acceptor of choice for conjugated polymer BHJ devices even though it does not form an optimal macroscopic network. The DFT calculations indicate that PCBM's superior local mobility comes from the near‐spherical nature of its molecular orbitals, which allow strong electronic coupling between adjacent molecules. In combination, DFT and TRMC techniques provide a tool for screening new fullerene derivatives for good local mobility when designing new molecules that can improve on the macroscopic electron mobility offered by PCBM.     

Distinguishing the Importance of Fullerene Phase Separation from Polymer Ordering in the Performance of Low Band Gap Polymer:Bis‐Fullerene Heterojunctions

One way to improve power conversion efficiency (PCE) of polymer based bulk‐heterojunction (BHJ) photovoltaic cells is to increase the open circuit voltage (V _oc). Replacing PCBM with bis‐adduct fullerenes significantly improves V _oc and the PCE in devices based on the conjugated polymer poly(3‐hexyl thiophene) (P3HT). However, for the most promising low band‐gap polymer (LBP) system, replacing PCBM with ICBA results in poor short‐circuit current (J _sc) and PCE although V _oc is significantly improved. The optimization of the morphology of as‐cast LBP/bis‐fullerene BHJ photovoltaics is attempted by adding a co‐solvent to the polymer/fullerene solution prior to film deposition. Varying the solubility of polymer and fullerene in the co‐solvent, bulk heterojunctions are fabricated with no change of polymer ordering, but with changes in fullerene phase separation. The morphologies of the as‐cast samples are characterized by small angle neutron scattering and neutron reflectometry. A homogenous dispersion of ICBA in LBP is found in the samples where the co‐solvent is selective to the polymer, giving poor device performance. Aggregates of ICBA are formed in samples where the co‐solvent is selective to ICBA. The resultant morphology improves PCE by up to 246%. A quantitative analysis of the neutron data shows that the interfacial area between ICBA aggregates and its surrounding matrix is improved, facilitating charge transport and improving the PCE.     

Time‐Dependent Morphology Evolution by Annealing Processes on Polymer:Fullerene Blend Solar Cells

Changes in the nanoscale morphologies of the blend films of poly (3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM), for high‐performance bulk‐heterojunction (BHJ) solar cells, are compared and investigated for two annealing treatments with different morphology evolution time scales, having special consideration for the diffusion and aggregation of PCBM molecules. An annealing condition with relatively fast diffusion and aggregation of the PCBM molecules during P3HT crystallization results in poor BHJ morphology because of prevention of the formation of the more elongated P3HT crystals. However, an annealing condition, accelerating PCBM diffusion after the formation of a well‐ordered morphology, results in a relatively stable morphology with less destruction of crystalline P3HT. Based on these results, an effective strategy for determining an optimized annealing treatment is suggested that considers the effect of relative kinetics on the crystallization of the components for a blend film with a new BHJ materials pair, upon which BHJ solar cells are based.     

Charge‐Separation Dynamics in Inorganic–Organic Ternary Blends for Efficient Infrared Photodiodes

Knowledge about the working mechanism of the PbS:P3HT:PCBM [P3HT=poly(3‐hexylthiophene), PCBM=[6,6]‐phenyl‐C₆₁ ‐butyric acid methyl ester] hybrid blend used for efficient near‐infrared photodiodes is obtained from time‐resolved photoluminescence (PL) studies. To understand the role of each component in the heterojunction, the PL dynamics of the ternary (PbS:P3HT:PCBM) blend and the binary (PbS:P3HT, PbS:PCBM and P3HT:PCBM) blends are compared with the PL of the pristine PbS nanocrystals (NCs) and P3HT. In the ternary blend the efficiency of the charge transfer is significantly enhanced compared to the one of PbS:P3HT and PbS:PCBM blends, indicating that both hole and electron transfer from excited NCs to the polymer and fullerene occur. The hole transfer towards the P3HT determines the equilibration of their population in the NCs after the electron transfer towards PCBM, allowing their re‐excitation and new charge transfer process.     

Efficient ternary polymer solar cells by optimizing photogenerated exciton dissociation and photon harvesting with a short wavelength absorption polymer acceptor as the third component

Ternary blend films, obtained by introducing a third component (a second acceptor as the third component) to a binary polymer solar cell (PSC), are a promising ternary strategy because the light absorption range, surface morphology, and charge carrier transport of the photoactive layer may be optimized, as can the energy level alignment between the donor and the acceptor. In this work, acceptors such as the short-wavelength-absorption polymer N2200 and the long-wavelength-absorption small molecule FOIC were combined with the donor PBDB-T-2F to construct ternary blends. The optimized ternary PSC could achieve a power conversion efficiency (PCE) of 13.98%, which is higher than the efficiencies of binary PSCs based on PBDB-T-2F:FOIC (12.65%) and PBDB-T-2F:N2200 (9.36%). The enhanced PCE of the ternary PSC is based on the high electron mobility, balanced charge transport, optimized surface morphology and charge carrier kinetics and the extended light absorption of the ternary photoactive layer, realized by adjusting the ratio of FOIC:N2200. Our results indicate that mixing a polymer acceptor into a binary photoactive layer to form a ternary blend photoactive layer is a valuable strategy for improving photovoltaic performance.     

Effect of Trace Solvent on the Morphology of P3HT:PCBM Bulk Heterojunction Solar Cells

The performance of bulk‐heterojunction (BHJ) solar cells is strongly correlated with the nanoscale structure of the active layer. Various processing techniques have been explored to improve the nanoscale morphology of the BHJ layer, e.g., by varying the casting solvent, thermal annealing, solvent annealing, and solvent additives. This paper highlights the role of residual solvent in the “dried” BHJ layer, and the effect of residual solvents on PCBM diffusion and ultimately the stability of the morphology. We show that solvent is retained within the BHJ film despite prolonged heat treatment, leading to extensive phase separation, as demonstrated by the growth in the size and quantity of PCBM agglomerates. The addition of a small volume fraction of nitrobenzene to the casting solution inhibits the diffusion of PCBM in the dry film, resulting in smaller PCBM agglomerates, and improves the fill factor of the BHJ device to 0.61 without further tempering. The addition of nitrobenzene also increases the P3HT crystalline content, while increasing the onset temperature for melting of P3HT side chains and backbone. The melting temperature for PCBM is also higher with the nitrobenzene additive present.     

Electrostatic Self‐Assembly Conjugated Polyelectrolyte‐Surfactant Complex as an Interlayer for High Performance Polymer Solar Cells

A simple method is demonstrated to improve the film‐forming properties and air stability of a conjugated polyelectrolyte (CPE) without complicated synthesis of new chemical structures. An anionic surfactant, sodium dodecybenzenesulfonate (SDS), is mixed with cationic CPEs. The electrostatic attraction between these two oppositely‐charged materials provides the driving force to form a stable CPE‐surfactant complex. Compared with a pure CPE, this electrostatic complex is not only compatible with highly hydrophobic bulk‐heterojunction (BHJ) films, e.g. poly(3‐hexylthiophene):[6,6]‐phenyl C₆₁ butyric acid methyl ester (P3HT:PCBM), but also works well with other low bandgap polymer‐based BHJ films. Using this complex as a cathode interface layer, a high power conversion efficiency of 4% can be obtained in P3HT:PCBM solar cells together with improved stability in air. Moreover, ～20% performance enhancement can also be achieved when the complex is used as an interlayer to replace calcium metal for low bandgap polymer‐based BHJ systems.     

Probing film solidification dynamics in polymer photovoltaics

Semiconducting conjugated polymers have drawn a great deal of attention over the past decade due to their solution processability and potential use in roll to roll fabrication of organic solar cells. Here, we report the effect of solvent vapor pressure on poly(3-hexylthiophene):[6,6]-phenyl C₆₁-butyric acid methyl ester (P3HT:PCBM) blade coated inverted solar cells using ZnO as the electron transporting layer and MoO₃ as the hole transporting layer. The resultant morphology and device performance are investigated for devices processed from solvents with varied vapor pressure and a mixed solvent. We report that the use of a mixed solvent system is advantageous for controlling the initial vapor pressure of the processing solution, thereby controlling the phase separated morphology between P3HT and PCBM which impacts ultimate solar cell performance.     

Additive‐Morphology Interplay and Loss Channels in “All‐Small‐Molecule” Bulk‐heterojunction (BHJ) Solar Cells with the Nonfullerene Acceptor IDTTBM

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 <1% can be achieved. Combining electron energy loss spectrum analyses in scanning transmission electron microscopy mode, carrier transport measurements via “metal‐insulator‐semiconductor carrier extraction” methods, and systematic recombination examinations by light‐dependence and transient photocurrent analyses, it is shown that DIO plays a determining role—establishing a favorable lengthscale for the phase‐separated SM donor–acceptor network and, in turn, improving the balance in hole/electron mobilities and the carrier collection efficiencies overall.     

Effect of Alkyl Side‐Chain Length on Photovoltaic Properties of Poly(3‐alkylthiophene)/PCBM Bulk Heterojunctions

The morphological, bipolar charge‐carrier transport, and photovoltaic characteristics of poly(3‐alkylthiophene) (P3AT):[6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) blends are studied as a function of alkyl side‐chain length m, where m equals the number of alkyl carbon atoms. The P3ATs studied are poly(3‐butylthiophene) (P3BT, m = 4), poly(3‐pentylthiophene) (P3PT, m = 5), and poly(3‐hexylthiophene) (P3HT, m = 6). Solar cells with these blends deliver similar order of photo‐current yield (exceeding 10 mA cm^?2) irrespective of side‐chain length. Power conversion efficiencies of 3.2, 4.3, and 4.6% are within reach using solar cells with active layers of P3BT:PCBM (1:0.8), P3PT:PCBM (1:1), and P3HT:PCBM (1:1), respectively. A difference in fill factor values is found to be the main source of efficiency difference. Morphological studies reveal an increase in the degree of phase separation with increasing alkyl chain length. Moreover, while P3PT:PCBM and P3HT:PCBM films have similar hole mobility, measured by hole‐only diodes, the hole mobility in P3BT:PCBM lowers by nearly a factor of four. Bipolar measurements made by field‐effect transistor showed a decrease in the hole mobility and an increase in the electron mobility with increasing alkyl chain length. Balanced charge transport is only achieved in the P3HT:PCBM blend. This, together with better processing properties, explains the superior properties of P3HT as a solar cell material. P3PT is proved to be a potentially competitive material. The optoelectronic and charge transport properties observed in the different P3AT:PCBM bulk heterojunction (BHJ) blends provide useful information for understanding the physics of BHJ films and the working principles of the corresponding solar cells.     

Molecular-weight-dependent nanoscale morphology in silole-containing cyclopentadithiophene polymer and fullerene derivative blends

We have investigated the effect of polymer molecular weight (MW) on the morphology and efficiency of bulk heterojunction (BHJ) solar cells comprised of poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(5,5′-thienyl-4,4′-dihexyl-2,2′-bithiazole)-2,6-diyl] (Si-PCPDTTBT) and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM). Striking morphological changes are observed in BHJ films upon the change of the polymer MW. Atomic force microscopy and transmission electron microscopy studies suggest that high MW polymer generated high degree of phase separation, leading to formation of an interpenetrating network for carrier transport. The X-ray diffraction investigation indicated that increased π–π stacking in Si-PCPDTTBT with increasing polymer MWs results in an increase in hole mobility of Si-PCPDTTBT and electron mobility of PCBM as well as the red shift absorption spectrum in BHJ films. The solar cells based on PCBM with high-MW Si-PCPDTTBT deliver power conversion efficiencies of 3.33%.     

Printable and Large‐Area Organic Solar Cells Enabled by a Ternary Pseudo‐Planar Heterojunction Strategy

Bulk heterojunction (BHJ) processing technology has had an irreplaceable role in the development of organic solar cells (OSCs) in the past decades due to the significant advantages in achieving high‐power conversion efficiency (PCE). However, the difficulty in exploring and regulating morphology makes it inadequate for upscaling large‐area OSCs. In this work, printable high‐performance ternary devices are fabricated by a pseudo‐planar heterojunction (PPHJ) strategy. The fullerene derivative indene‐C₆₀ bisadduct (ICBA) is incorporated into PM6/IT‐4F system to expand the vertical phase separation and facilitate an obvious PPHJ structure. After the addition of ICBA, the IT‐4F enriches on the surface of active layer, while PM6 is accumulated underneath. Furthermore, it increases the crystallinity of PM6, which facilitates exciton dissociation and charge transfer. Accordingly, 1.05 cm² devices are fabricated by blade‐coating with an enhanced PCE of 14.25% as compared to the BHJ devices (13.73%). The ternary PPHJ strategy provides an effective way to optimize the vertical phase separation of organic semiconductor during scalable printing methods.     

Measuring Domain Sizes and Compositional Heterogeneities in P3HT‐PCBM Bulk Heterojunction Thin Films with 1H Spin Diffusion NMR Spectroscopy

The application of ¹H spin diffusion nuclear magnetic resonance (NMR) is expanded to polymer‐fullerene blends for bulk heterojunction (BHJ) organic photovoltaics (OPV) by developing a new experimental methodology for measuring the thin films used in poly‐3‐hexylthiophene–phenyl C61‐butyric acid methyl ester (P3HT‐PCBM) OPV devices and by creating an analysis framework for estimating domain size distributions. It is shown that variations in common P3HT‐PCBM BHJ processing parameters such as spin‐coating speed and thermal annealing can significantly affect domain size distributions, which in turn affect power conversion efficiency. ¹H spin diffusion NMR analysis reveals that films spin‐cast at fast speeds in dichlorobenzene are primarily composed of small (<10 nm) domains of each component; these devices exhibit low power conversion efficiencies (η = 0.4%). Fast‐cast films improve substantially by thermal annealing, which causes nanometer‐scale coarsening leading to higher efficiency (η = 2.2%). Films spin‐cast at slow speeds and then slowly dried exhibit larger domains and even higher efficiencies (η = 2.6%), but do not benefit from thermal annealing. The ¹H spin diffusion NMR results show that a significant population of domains tens of nanometers in size is a common characteristic of samples with higher efficiencies.