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.     

Abrupt Morphology Change upon Thermal Annealing in Poly(3‐Hexylthiophene)/Soluble Fullerene Blend Films for Polymer Solar Cells

The in situ morphology change upon thermal annealing in bulk heterojunction blend films of regioregular poly(3‐hexylthiophene) (P3HT) and 1‐(3‐methoxycarbonyl)‐propyl‐1‐phenyl‐(6,6)C₆₁ (PCBM) is measured by a grazing incidence X‐ray diffraction (GIXD) method using a synchrotron radiation source. The results show that the film morphology—including the size and population of P3HT crystallites—abruptly changes at 140 °C between 5 and 30 min and is then stable up to 120 min. This trend is almost in good agreement with the performance change of polymer solar cells fabricated under the same conditions. The certain morphology change after 5 min annealing at 140 °C is assigned to the on‐going thermal transition of P3HT molecules in the presence of PCBM transition. Field‐emission scanning electron microscopy measurements show that the crack‐like surface of blend films becomes smaller after a very short annealing time, but does not change further with increasing annealing time. These findings indicate that the stability of P3HT:PCBM solar cells cannot be secured by short‐time annealing owing to the unsettled morphology, even though the resulting efficiency is high.     

Precise Structural Development and its Correlation to Function in Conjugated Polymer: Fullerene Thin Films by Controlled Solvent Annealing

The impact of controlled solvent vapor exposure on the morphology, structural evolution, and function of solvent‐processed poly(3‐hexylthiophene):[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (P3HT:PCBM) bilayers is presented. Grazing incident wide angle X‐ray scattering (GIWAXS) shows that the crystallization of P3HT increases with solvent exposure, while neutron reflectivity shows that P3HT simultaneously diffuses into PCBM, indicating that an initial bilayer structure evolves into a bulk heterojunction structure. Small angle neutron scattering (SANS) shows the agglomeration of PCBM and the formation of a PCBM pure phase when solvent annealing for 90 min. The structural evolution can be described as occurring in two stages: the first stage combines the enhanced crystallization of P3HT and diffusion of PCBM into P3HT, while the second stage entails the agglomeration of PCBM and formation of a PCBM pure phase. The phase separation of PCBM from P3HT is not driven by P3HT crystallinity, but is due to the concentration of PCBM exceeding the miscibility limit of PCBM in P3HT. Correlation of the morphology to photovoltaic activity shows that device performance significantly improves with solvent annealing for 90 min, indicating that both sufficient P3HT crystallization and formation of a PCBM pure phase are crucial in the optimization of the morphology of the active layer.     

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.     

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.     

Crystallization‐Induced Phase Separation in Solution‐Processed Small Molecule Bulk Heterojunction Organic Solar Cells

The driving forces and processes associated with the development of phase separation upon thermal annealing are investigated in solution‐processed small molecule bulk heterojunction (BHJ) organic solar cells utilizing a diketopyrrolopyrrole‐based donor molecule and a fullerene acceptor (PCBM). In‐situ thermal annealing X‐ray scattering is used to monitor the development of thin film crystallization and phase separation and reveals that the development of blend phase separation strongly correlates with the nucleation of donor crystallites. Additionally, these morphological changes lead to dramatic increases in blend electron mobility and solar cell figures of merit. These results indicate that donor crystallization is the driving force for blend phase separation. It is hypothesized that donor crystallization from an as‐cast homogeneous donor:acceptor blend simultaneously produces donor‐rich domains, consisting largely of donor crystallites, and acceptor‐rich domains, formed from previously mixed regions of the film that have been enriched with acceptor during donor crystallization. Control of donor crystallization in solution‐processed small molecule BHJ solar cells employing PCBM is thus emphasized as an important strategy for the engineering of the nanoscale phase separated, bicontinuous morphology necessary for the fabrication of efficient BHJ photovoltaic devices.     

Cover Picture: Tuning the Dimensions of C60‐Based Needlelike Crystals in Blended Thin Films (Adv. Funct. Mater. 6/2006)

A new ordered structure of the C₆₀ derivative PCBM is obtained in thin films based on the blend PCBM:P3HT, as detailed by Swinnen, Manca, and co‐workers on p. 760. Needlelike crystalline PCBM structures, whose dimensions and spatial distribution ca be tuned by adjusting the blend ratio and annealing conditions, are formed. In typical solar‐cell applications of these blended films, these results indicate that during long‐term operation under normal conditions (50–70 °C) morphology changes and a decrease in cell performance could occur. A new ordered structure of the C₆₀ derivative PCBM ([6‐6]‐phenyl C₆₁‐butyric acid methyl ester) is obtained in thin films based on the blend PCBM:regioregular P3HT (poly(3‐hexylthiophene)). Rapid formation of needlelike crystalline PCBM structures of a few micrometers up to 100 μm in size is demonstrated by submitting the blended thin films to an appropriate thermal treatment. These structures can grow out to a 2D network of PCBM needles and, in specific cases, to spectacular PCBM fans. Key parameters to tune the dimensions and spatial distribution of the PCBM needles are blend ratio and annealing conditions. The as‐obtained blended films and crystals are probed using atomic force microscopy, transmission electron microscopy, selected area electron diffraction, optical microscopy, and confocal fluorescence microscopy. Based on the analytical results, the growth mechanism of the PCBM structures within the film is described in terms of diffusion of PCBM towards the PCBM crystals, leaving highly crystalline P3HT behind in the surrounding matrix.     

Solvent‐Induced Morphology in Polymer‐Based Systems for Organic Photovoltaics

Studies on the influence of four different solvents on the morphology and photovoltaic performance of bulk‐heterojunction films made of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁ butyric acid methyl ester (PCBM) via spin‐coating for photovoltaic applications are reported. Solvent‐dependent PCBM cluster formation and P3HT crystallization during thermal annealing are investigated with optical microscopy and grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) and are found to be insufficient to explain the differences in device performance. A combination of atomic force microscopy (AFM), X‐ray reflectivity (XRR), and grazing‐incidence small‐angle X‐ray scattering (GISAXS) investigations results in detailed knowledge of the inner film morphology of P3HT:PCBM films. Vertical and lateral phase separation occurs during spin‐coating and annealing, depending on the solvent used. The findings are summarized in schematics and compared with the IV characteristics. The main influence on the photovoltaic performance arises from the vertical material composition and the existence of lateral phase separation fitting to the exciton diffusion length. Absorption and photoluminescence measurements complement the structural analysis.     

Semiconducting Carbon Nanotubes for Improved Efficiency and Thermal Stability of Polymer–Fullerene Solar Cells

The effects of the incorporation of semiconducting single‐walled nanotubes (sc‐SWNTs) with high purity on the bulk heterojunction (BHJ) organic solar cell (OSC) based on regioregular poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (rr‐P3HT:PCBM) are reported for the first time. The sc‐SWNTs induce the organization of the polymer phase, which is evident from the increase in crystallite size, the red‐shifted absorption characteristics and the enhanced hole mobility. By incorporating sc‐SWNTs, OSC with a power conversion efficiency (PCE) as high as 4% can be achieved, which is ≈8% higher than our best control device. A novel application of sc‐SWNTs in improving the thermal stability of BHJ OSCs is also demonstrated. After heating at 150 °C for 9 h, it is observed that the thermal stability of rr‐P3HT:PCBM devices improves by more than fivefold with inclusion of sc‐SWNTs. The thermal stability enhancement is attributed to a more suppressed phase separation, as shown by the remarkable decrease in the formation of sizeable crystals, which in turn can be the outcome of a more controlled crystallization of the blend materials on the nanotubes.     

Poly(3-hexylthiophene) nanofiber networks for enhancing the morphology stability of polymer solar cells

A stable morphology in the photoactive layer is a prerequisite for increasing the lifetime of organic solar cells. Intense research efforts focusing on this research topic have typically resorted to complicated synthetic methods to reach this goal. Herein, the authors present a facile approach to directly achieve efficient polymer solar cells with a remarkably enhanced thermally stable morphology by constructing densely distributed poly(3-hexylthiophene) (P3HT) nanofibers in the pristine composite films with PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) from solution without any post treatments. Controlled experiments reveal that the presence of numerous preformed P3HT nanofibers in the pristine films, with much larger size than P3HT and PCBM molecules, provides a fixed and rigid network to spatially confine the diffusion of PCBM molecules during thermal annealing, thus preventing the formation of large-scale PCBM crystals. This simple method represents a “one-step” way to prepare high performance photovoltaic devices with thermally stable morphologies and no necessary post treatments.     

High‐Resolution Spectroscopic Mapping of the Chemical Contrast from Nanometer Domains in P3HT:PCBM Organic Blend Films for Solar‐Cell Applications

A high‐resolution near‐field spectroscopic mapping technique is successfully applied to investigate the influence of thermal annealing on the morphology of a poly(3‐hexylthiophene) and [6,6]‐penyl‐C₆₁ butyric acid methyl ester (P3HT:PCBM) blend film. Based on the simultaneously recorded morphological and spectroscopic information, the interplay among the blend film morphology, the local P3HT:PCBM molecular distribution, and the P3HT photoluminescence (PL) quenching efficiency are systematically discussed. The PL and Raman signals of the electron donor (P3HT) and acceptor (PCBM) are probed at an optical resolution of approximately 10 nm, which allows the chemical nature of the different domains to be identified directly. In addition, the local PL quenching efficiency, which is related to the electron transfer from P3HT to PCBM, is quantitatively revealed. From these experimental results, it is proposed that high‐resolution near‐field spectroscopic imaging is capable of mapping the local chemical composition and photophysics of the P3HT:PCBM blends on a scale of a few nanometers.     

Stabilization of poly(3-hexylthiophene)/PCBM morphology by hydroxyl group end-functionalized P3HT and its application to polymer solar cells

A new concept to stabilize the morphology of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) blend through H-bond formation by using a hydroxyl group end-functionalized P3HT (HOC-P3HT-COH) as a compatibilizer is presented. Domain size of the PCBM crystals in the annealed P3HT/PCBM film is diminished with addition of HOC-P3HT-COH. Surface roughness of the P3HT/PCBM film also becomes smoother with addition of HOC-P3HT-COH. Thermal stability of solar cell device is improved significantly through the H-bond formation between HOC-P3HT-COH and PCBM. A high performance and thermal stable polymer solar cell with 4.06% power conversion efficiency under AM1.5G irradiation is fabricated with 5% HOC-P3HT-COH in P3HT/PCBM layer.     

Effect of Carbon Chain Length in the Substituent of PCBM‐like Molecules on Their Photovoltaic Properties

A series of [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM)‐like fullerene derivatives with the butyl chain in PCBM changing from 3 to 7 carbon atoms, respectively (F1–F5), are designed and synthesized to investigate the relationship between photovoltaic properties and the molecular structure of fullerene derivative acceptors. F2 with a butyl chain is PCBM itself for comparison. Electrochemical, optical, electron mobility, morphology, and photovoltaic properties of the molecules are characterized, and the effect of the alkyl chain length on their properties is investigated. Although there is little difference in the absorption spectra and LUMO energy levels of F1–F5, an interesting effect of the alkyl chain length on the photovoltaic properties is observed. For the polymer solar cells (PSCs) based on P3HT as donor and F1–F5, respectively, as acceptors, the photovoltaic behavior of the P3HT/F1 and P3HT/F4 systems are similar to or a little better than that of the P3HT/PCBM device with power conversion efficiencies (PCEs) above 3.5%, while the performances of P3HT/F3 and P3HT/F5‐based solar cells are poorer, with PCE values below 3.0%. The phenomenon is explained by the effect of the alkyl chain length on the absorption spectra, fluorescence quenching degree, electron mobility, and morphology of the P3HT/F1–F5 (1:1, w/w) blend films.     

The Effect of Thermal Treatment on the Morphology and Charge Carrier Dynamics in a Polythiophene–Fullerene Bulk Heterojunction

The influence of various thermal treatment steps on the morphology and the photoconductive properties of a non‐contacted, 50 nm thick blend (50:50 wt.‐%) of [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) and poly(3‐hexyl thiophene) (P3HT) spin‐coated from chloroform has been studied using transmission electron microscopy (TEM) and the electrodeless time‐resolved microwave conductivity technique. After annealing the film for 5 min at 80 °C, TEM images show the formation of crystalline fibrils of P3HT due to a more ordered packing of the polymer chains. The thermal treatment results in a large increase of the photoconductivity, due to an enhancement of the hole mobility in these crystalline P3HT domains from 0.0056 cm² V^–1 s ^–1 for the non‐annealed sample to 0.044 cm² V^–1 s ^–1 for the sample annealed at 80 °C. In contrast, the temporal shape of the photoconductivity, with typical decay half‐times, τ_1/2, of 1 μs for the lowest excitation intensities, is unaffected by the temperature treatment. Further annealing of the sample at 130 °C results in the formation of three different substructures within the heterojunction: a PCBM:P3HT blend with PCBM‐rich clusters, a region depleted of PCBM, and large PCBM single crystals. Only a minor increase in the amplitude, but a tenfold rise of the decay time of the photoconductivity, is observed. This is explained by the formation of PCBM‐rich clusters and large PCBM single crystals, resulting in an increased diffusional escape probability for mobile charge carriers and hence reduced recombination.     

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.     

Tuning the Dimensions of C60‐Based Needlelike Crystals in Blended Thin Films

A new ordered structure of the C₆₀ derivative PCBM ([6‐6]‐phenyl C₆₁‐butyric acid methyl ester) is obtained in thin films based on the blend PCBM:regioregular P3HT (poly(3‐hexylthiophene)). Rapid formation of needlelike crystalline PCBM structures of a few micrometers up to 100 μm in size is demonstrated by submitting the blended thin films to an appropriate thermal treatment. These structures can grow out to a 2D network of PCBM needles and, in specific cases, to spectacular PCBM fans. Key parameters to tune the dimensions and spatial distribution of the PCBM needles are blend ratio and annealing conditions. The as‐obtained blended films and crystals are probed using atomic force microscopy, transmission electron microscopy, selected area electron diffraction, optical microscopy, and confocal fluorescence microscopy. Based on the analytical results, the growth mechanism of the PCBM structures within the film is described in terms of diffusion of PCBM towards the PCBM crystals, leaving highly crystalline P3HT behind in the surrounding matrix.     

P3HT/PCBM Bulk Heterojunction Solar Cells: Impact of Blend Composition and 3D Morphology on Device Performance

The performance of polymer solar cells (PSC) strongly depends on the 3D morphological organization of the donor and acceptor compounds within the bulk heterojunction active layer. The technique of electron tomography is a powerful tool for studying 3D morphology of the layers composed of poly(3‐hexylthiophene) (P3HT) and a fullerene derivative ([6,6]‐phenyl‐C61‐butyric acid methyl ester; PCBM), especially to quantify the amount and distribution of fibrillar P3HT nanocrystals throughout the volume of the active layer. In this study, electron tomography is used to characterize P3HT/PCBM layers with different blend compositions, both before and after thermal annealing. The power conversion efficiency of the corresponding PSCs is strongly dependent on the overall crystallinity of P3HT and the way P3HT crystals are distributed throughout the thickness of the active layer.     

Laser-induced crystallization and conformation control of poly(3-hexylthiophene) for improving the performance of organic solar cells

Femto-second laser irradiation on P3HT:PCBM solutions have been demonstrated to have a significant impact on the conformational structures and photovoltaic performance of the resultant thin films. The crystallinity and edge-on/face-on conformations of P3HT and the aggregation of PCBM can be manipulated by controlling the wavelength (400–800 nm) and illumination duration (1–3 h) of the lasers. Grazing incidence wide- and small-angle X-ray scattering (GIWAXS and GISAXS) have been simultaneously utilized to characterize the nanostructures of the P3HT:PCBM blend films spin-cast from pristine and laser-irradiated solutions. The results show that the crystallinity, π-π* stacking and face-on conformations of P3HT can be enhanced as a result of the laser irradiation at 500 nm for 3 h. Furthermore, the diffusion and aggregation of PCBM molecules are suppressed by the photo-induced dimerization, as evidenced by the Raman spectra of the films cast from laser-irradiated PCBM solutions. The time-resolved fluorescence decay profiles show the charge transfer efficiency is improved, which may correlate to the supramolecular ordering of the polythiophene chains and the optimized phase separation in P3HT:PCBM composite. In the P3HT:PCBM active layer of the organic solar cells, more efficient charge transport and fine interpenetrating networks can be achieved due to the improved conformational microstructures. Consequently, the short-circuit current densities and power conversion efficiencies can be enhanced in organic solar cells based on the laser-irradiation processed P3HT:PCBM solutions.     

Evolution of Structure,Optoelectronic Properties,and Device Performance of Polythiophene:Fullerene Solar Cells During Thermal Annealing

We use spectroscopic ellipsometry to study the evolution of structure and optoelectronic properties of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C61‐butyric acid methyl ester (PCBM) photovoltaic thin film blends upon thermal annealing. Four distinct processes are identified: the evaporation of residual solvent above the glass transition temperature of the blend, the relaxation of non‐equilibrium molecular conformation formed through spin‐casting, the crystallization of both P3HT and PCBM components, and the phase separation of the P3HT and PCBM domains. Devices annealed at 150 °C for between 10 and 60 min exhibit an average power conversion efficiency of around 4.0%. We find that the rate at which the P3HT/PCBM is returned to room temperature is more important in determining device efficiency than the duration of the isothermal annealing process. We conclude that the rapid quenching of a film from the annealing temperature to room temperature hampers the crystallization of the P3HT and can trap non‐equilibrium morphological states. Such states apparently impact on device short circuit current, fill factor and, thus, operational efficiency.     

Effects of Annealing on the Nanomorphology and Performance of Poly(alkylthiophene):Fullerene Bulk‐Heterojunction Solar Cells

The evolution of nanomorphology within thin solid‐state films of poly(3‐alkylthiophene):[6,6]‐phenyl‐C₆₁ butyric acid methyl ester (P3AT:PCBM) blends during the film formation and subsequent thermal annealing is reported. In detail, the influence of the P3AT's alkyl side chain length on the polymer/fullerene phase separation is discussed. Butyl, hexyl, octyl, decyl, and dodecyl side groups are investigated. All of the P3ATs used were regioregular. To elucidate the nanomorphology, atomic force microscopy (AFM), X‐ray diffraction, and optical spectroscopy are applied. Furthermore, photovoltaic devices of each of the different P3ATs have been constructed, characterized, and correlated with the nanostructure of the blends. It is proposed that the thermal‐annealing step, commonly applied to these P3AT:PCBM blend films, controls two main issues at the same time: a) the crystallization of P3AT and b) the phase separation and diffusion of PCBM. The results show that PCBM diffusion is the main limiting process for reaching high device performances.