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.     

Effects of processing additive on bipolar field-effect transistors based on blends of poly(3-hexylthiophene) and fullerene bearing long alkyl tails

Bipolar FETs (BiFETs) based on the bulk heterojunction system comprised of various ratios of P3HT and soluble fullerene derivatives are demonstrated. We studied the effect of addition of small concentrations of the processing additive, 1,8-octanedithiol (ODT), on gate-induced transport properties. The control blend system consisting of poly (3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) showed enhanced hole transport properties with the addition of the ODT additive. However, electron transport properties were diminished in the presence of ODT additive because of the relatively isolated PCBM phase between the large-scale segregation of the P3HT amorphous phase. The BHJ BiFET based on P3HT and soluble fullerene derivatives bearing long alkyl tails (FP-Ph-OC10) showed enhanced performance in both hole and electron transport when the ODT additive was applied. We attribute the enhancement of hole mobility to well-formed P3HT fibrilla structures of P3HT caused by the alkyl–alkyl interaction assisted by both the ODT additive and alkyl side chain in FP-Ph-OC10. As the P3HT forms fibrilla structures, connection to the isolated FP-Ph-OC10 phase be formed, resulting in a continuous electron pathway, thereby improving electron mobility. This suggests that not only the selective solubility, but also the alkyl-alkyl interaction between the side-chain and ODT additive may affect the phase segregation of BHJ mixtures.     

Mechanical Properties of Conjugated Polymers and Polymer‐Fullerene Composites as a Function of Molecular Structure

Despite the importance of mechanical compliance in most applications of semiconducting polymers, the effects of structural parameters of these materials on their mechanical properties are typically not emphasized. This paper examines the effect of length of the pendant group on the tensile modulus and brittleness for a series of regioregular poly(3‐alkylthiophenes) (P3ATs) and their blends with a soluble fullerene derivative, PCBM. The tensile modulus decreases with increasing length of the alkyl side‐chain, from 1.87 GPa for butyl side chains to 0.16 GPa for dodecyl chains. The moduli of P3AT:PCBM blends films are greater than those of the pure polymers by factors of 2–4. A theoretical model produces a trend in the effect of alkyl side chain on tensile modulus that follows closely to the experimental measurements. Tensile modulus correlates with brittleness, as the strain at which cracks appear is 6% for P3BT and >60% for P3OT. Adhesion of the P3AT film to a polydimethylsiloxane (PDMS) substrate is believed to play a role in an apparent increase in brittleness from P3OT to P3DDT. The additive 1,8‐Diiodooctane (DIO) reduces the modulus of P3HT:PCBM blend by a factor of 3. These results could enable mechanically robust, flexible, and stretchable electronics.     

Charge Transport and Photocurrent Generation in Poly(3‐hexylthiophene): Methanofullerene Bulk‐Heterojunction Solar Cells

The effect of controlled thermal annealing on charge transport and photogeneration in bulk‐heterojunction solar cells made from blend films of regioregular poly(3‐hexylthiophene) (P3HT) and methanofullerene (PCBM) has been studied. With respect to the charge transport, it is demonstrated that the electron mobility dominates the transport of the cell, varying from 10^–8 m² V^–1 s^–1 in as‐cast devices to ≈3 × 10^–7 m² V^–1 s^–1 after thermal annealing. The hole mobility in the P3HT phase of the blend is dramatically affected by thermal annealing. It increases by more than three orders of magnitude, to reach a value of up to ≈ 2 × 10^–8 m² V^–1 s^–1 after the annealing process, as a result of an improved crystallinity of the film. Moreover, upon annealing the absorption spectrum of P3HT:PCBM blends undergo a strong red‐shift, improving the spectral overlap with solar emission, which results in an increase of more than 60 % in the rate of charge‐carrier generation. Subsequently, the experimental electron and hole mobilities are used to study the photocurrent generation in P3HT:PCBM devices as a function of annealing temperature. The results indicate that the most important factor leading to a strong enhancement of the efficiency, compared with non‐annealed devices, is the increase of the hole mobility in the P3HT phase of the blend. Furthermore, numerical simulations indicate that under short‐circuit conditions the dissociation efficiency of bound electron–hole pairs at the donor/acceptor interface is close to 90 %, which explains the large quantum efficiencies measured in P3HT:PCBM blends.     

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.     

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.     

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.     

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.     

Alkyl‐Chain‐Length‐Independent Hole Mobility via Morphological Control with Poly(3‐alkylthiophene) Nanofibers

The field‐effect transistor (FET) and diode characteristics of poly(3‐alkylthiophene) (P3AT) nanofiber layers deposited from nanofiber dispersions are presented and compared with those of layers deposited from molecularly dissolved polymer solutions in chlorobenzene. The P3AT n‐alkyl‐side‐chain length was varied from 4 to 9 carbon atoms. The hole mobilities are correlated with the interface and bulk morphology of the layers as determined by UV–vis spectroscopy, transmission electron microscopy (TEM) with selected area electron diffraction (SAED), atomic force microscopy (AFM), and polarized carbon K‐edge near edge X‐ray absorption fine structure (NEXAFS) spectroscopy. The latter technique reveals the average polymer orientation in the accumulation region of the FET at the interface with the SiO₂ gate dielectric. The previously observed alkyl‐chain‐length‐dependence of the FET mobility in P3AT films results from differences in molecular ordering and orientation at the dielectric/semiconductor interface, and it is concluded that side‐chain length does not determine the intrinsic mobility of P3ATs, but rather the alkyl chain length of P3ATs influences FET diode mobility only through changes in interfacial bulk ordering in solution processed films.     

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.     

Photoconductivity of a Low‐Bandgap Conjugated Polymer

The photoconductive properties of a novel low‐bandgap conjugated polymer, poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)], PCPDTBT, with an optical energy gap of E_g ～ 1.5 eV, have been studied. The results of photoluminescence and photoconductivity measurements indicate efficient electron transfer from PCPDTBT to PCBM ([6,6]‐phenyl‐C61 butyric acid methyl ester, a fullerene derivative), where PCPDTBT acts as the electron donor and PCBM as the electron acceptor. Electron‐transfer facilitates charge separation and results in prolonged carrier lifetime, as observed by fast (t > 100 ps) transient photoconductivity measurements. The photoresponsivities of PCPDTBT and PCPDTBT:PCBM are comparable to those of poly(3‐hexylthiophene), P3HT, and P3HT:PCBM, respectively. Moreover, the spectral sensitivity of PCPDTBT:PCBM extends significantly deeper into the infrared, to 900 nm, than that of P3HT. The potential of PCPDTBT as a material for high‐efficiency polymer solar cells is discussed.     

Enhanced Thermal Stability and Efficiency of Polymer Bulk‐Heterojunction Solar Cells by Low‐Temperature Drying of the Active Layer

This study addresses two key issues, stability and efficiency, of polymer solar cells based on blended poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) by demonstrating a film‐forming process that involves low‐temperature drying (?5 °C) and subsequent annealing of the active layer. The low‐temperature process achieves 4.70% power conversion efficiency (PCE) and ～1250 h storage half‐life at 65 °C, which are significant improvements over the 3.39% PCE and ～143 h half‐life of the regular room‐temperature process. The improvements are attributed to the enhanced nucleation of P3HT crystallites as well as the minimized separation of the P3HT and PCBM phases at the low drying temperature, which upon post‐drying annealing results in a morphology consisting of small PCBM‐rich domains interspersed within a densely interconnected P3HT crystal network. This morphology provides ample bulk‐heterojunction area for charge generation while allowing for facile charge transport; moreover, the P3HT crystal network serves as an immobile frame at heating temperatures less than the melting point (T_m) of P3HT, thus preventing PCBM/P3HT phase separation and the corresponding device degradation.     

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.     

Compositional Dependence of the Performance of Poly(p‐phenylene vinylene):Methanofullerene Bulk‐Heterojunction Solar Cells

The dependence of the performance of OC₁C₁₀‐PPV:PCBM (poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐p‐phenylene vinylene):methanofullerene [6,6]‐phenyl C₆₁‐butyric acid methyl ester)‐based bulk heterojunction solar cells on their composition has been investigated. With regard to charge transport, we demonstrate that the electron mobility gradually increases on increasing the PCBM weight ratio, up to 80 wt.‐%, and subsequently saturates to its bulk value. Surprisingly, the hole mobility in the PPV phase shows an identical behavior and saturates beyond 67 wt.‐% PCBM, a value which is more than two orders of magnitude higher than that of the pure polymer. The experimental electron and hole mobilities were used to study the photocurrent generation of OC₁C₁₀‐PPV:PCBM bulk‐heterojunction (BHJ) solar cells. From numerical calculations, it is shown that for PCBM concentrations exceeding 80 wt.‐% reduced light absorption is responsible for the loss of device performance. From 80 to 67 wt.‐%, the decrease in power conversion efficiency is mainly due to a decreased separation efficiency of bound electron–hole (e–h) pairs. Below 67 wt.‐%, the performance loss is governed by a combination of a reduced generation rate of e–h pairs and a strong decrease in hole transport.     

Optical,electrical and mechanical properties of indium tin oxide on polyethylene terephthalate substrates: Application in bulk-heterojunction polymer solar cells

We investigated optical, electrical and mechanical properties of indium tin oxide (ITO) on flexible polyethylene terephthalate (PET) substrate, considering bulk-heterojunction (BHJ) polymer solar cells applications. Encapsulation of flexible solar cells with the architecture PET/ITO/PEDOT:PSS/P3HT:PCBM (or P3HT:PCBM:AZ-NDI-4)/Al was done by direct brush-painting with nail enamel. Active cell layer blends of [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) with regioregular or regiorandom poly(3-hexylthiophene-2,5-diyl) (P3HT) were applied. Additionally for this role the mixture of regioregular P3HT:PCBM with naphthalene diimide–imine with four thiophene rings AZ-NDI-4 was tested. Obtained photovoltaic (PV) and optical (UV–vis) results of the flexible polymer solar cells were compared with the same architecture of devices on the glass/ITO substrate.     

Annealing‐Free High Efficiency and Large Area Polymer Solar Cells Fabricated by a Roller Painting Process

Polymer solar cells are fabricated by a novel solution coating process, roller painting. The roller‐painted film – composed of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) – has a smoother surface than a spin‐coated film. Since the roller painting is accompanied by shear and normal stresses and is also a slow drying process, the process effectively induces crystallization of P3HT and PCBM. Both crystalline P3HT and PCBM in the roller‐painted active layer contribute to enhanced and balanced charge‐carrier mobility. Consequently, the roller‐painting process results in a higher power conversion efficiency (PCE) of 4.6%, as compared to that for spin coating (3.9%). Furthermore, annealing‐free polymer solar cells (PSCs) with high PCE are fabricated by the roller painting process with the addition of a small amount of octanedi‐1,8‐thiol. Since the addition of octanedi‐1,8‐thiol induces phase separation between P3HT and PCBM and the roller‐painting process induces crystallization of P3HT and PCBM, a PCE of roller‐painted PSCs of up to 3.8% is achieved without post‐annealing. A PCE of over 2.7% can also be achieved with 5 cm² of active area without post‐annealing.     

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.     

High‐Efficiency Organic Solar Cells Based on Preformed Poly(3‐hexylthiophene) Nanowires

Bulk heterojunction solar cells based on blends of poly(3‐hexylthiophene) (P3HT) and phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) are fabricated using self‐assembled P3HT nanowires in a marginal solvent without post‐treatments. The interconnected network structures of self‐organized P3HT nanowires create continuous percolation pathways through the active layer and contribute to enhanced carrier mobility. The morphology and photovoltaic properties are studied as a function of ageing time of the P3HT precursor solution. Optimal photovoltaic properties are found at 60 h ageing time, which increases both light absorption and charge balance. Multilayered solar cells with a compositionally graded structure are fabriacted using preformed P3HT nanowires by inserting a pure P3HT donor phase onto the hole‐collecting electrode. Applying optimized annealing conditions to the P3HT buffer layer achieves an enhanced hole mobility and a power conversion efficiency of 3.94%. The introduction of a compositionally graded device structure, which contains a P3HT‐only region, reduces charge recombination and electron injection to the indium tin oxide (ITO) electrode and enhances the device properties. These results demonstrate that preformed semiconductor nanowires and compositionally graded structures constitute a promising approach to the control of bulk heterojunction morphology and charge‐carrier mobility.     

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.     

Poly(3-hexylthiophene) coated graphene oxide for improved performance of bulk heterojunction polymer solar cells

An effective method for preparing poly(3-hexylthiophene) (P3HT) coated graphene oxide (GO), (P-GO), based on an ethanol mediated mixing and solvent evaporation method is described. P-GO exhibits good dispersibility in the non-polar solvent o-dichlorobenzene (DCB) allowing the preparation of polymer blend composites. P-GO was doped into P3HT: PCBM blends by solution mixing and shown to facilitate phase separation of P3HT and PCBM in P3HT: PCBM blend films to achieve a more optimum morphology for polymer photovoltaic cells. Bulk heterojunction P3HT: PCBM solar cells exhibit ∼18% power conversion efficiency enhancement in the presence of P-GO.