PCBM Molecules Research Articles

Self-assembled PCBM bilayers on graphene and HOPG examined by AFM and STM

In this work we report fabrication and characterization of phenyl-C61-butyric acid methyl ester (PCBM) bilayer structures on graphene and highly oriented pyrolytic graphite (HOPG). Through careful control of the PCBM solution concentration (from 0.1 to 2 mg ml−1) and the deposition conditions, we demonstrate that PCBM molecules self-assemble into bilayer structures on graphene and HOPG substrates. Interestingly, the PCBM bilayers are formed with two distinct heights on HOPG, but only one unique representative height on graphene. At elevated annealing temperatures, edge diffusion allows neighboring vacancies to merge into a more ordered structure. This is, to the best of our knowledge, the first experimental realization of PCBM bilayer structures on graphene. This work could provide valuable insight into fabrication of new hybrid, ordered structures for applications to organic solar cells.

Bulk Heterojunction Solar Cells: Impact of Minor Structural Modifications to the Polymer Backbone on the Polymer–Fullerene Mixing and Packing and on the Fullerene–Fullerene Connecting Network

AbstractThe morphology of the active layer of a bulk heterojunction solar cell, made of a blend of an electron‐donating polymer and an electron‐accepting fullerene derivative, is known to play a determining role in device performance. Here, a combination of molecular dynamics simulations and long‐range corrected density functional theory calculations is used to elucidate the molecular‐scale effects that even minor structural changes to the polymer backbone can have on the “local” morphology; this study focuses on the extent of polymer–fullerene mixing, on their packing, and on the characteristics of the fullerene–fullerene connecting network in the mixed regions, aspects that are difficult to access experimentally. Three representative polymer donors are investigated: (i) poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3′″‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2′″‐quaterthiophen‐5,5′″‐diyl)] (PffBT4T‐2OD); (ii) poly[(2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3′″‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2′″‐quaterthiophen‐5,5′″‐diyl)] (PBT4T‐2OD), where the fluorine atoms in the benzothiadiazole moieties of PffBT4T‐2OD are replaced with hydrogen atoms; and (iii) poly[(2,2′‐bithiophene)‐alt‐(4,7‐bis((2‐decyltetradecyl)thiophen‐2‐yl)‐5,6‐difluoro‐2‐propyl‐2H‐benzo[d][1,2,3]triazole)] (PT2‐FTAZ), where the sulfur atoms in the benzothiadiazole moieties of PffBT4T‐2OD are replaced with nitrogen atoms carrying a linear C3H7 side‐chain; these polymers are mixed with the phenyl‐C71‐butyric acid methyl ester (PC71BM) acceptor. This study also discusses the nature of the charge‐transfer electronic states appearing at the donor–acceptor interfaces, the electronic couplings relevant for the charge‐recombination process, and the electron‐transfer features between neighboring PC71BM molecules.

Analysis of Ion‐Diffusion‐Induced Interface Degradation in Inverted Perovskite Solar Cells via Restoration of the Ag Electrode

AbstractStraightforward evidence for ion‐diffusion‐induced interfacial degradation in inverted perovskite solar cells is presented. Over 1000 h, solar cells inevitably undergo degradation, especially with respect to the current density and fill factor. The Ag electrode is peeled off and re‐evaporated to investigate the effect of the Ag/[6,6]‐phenyl C71 butyric acid methyl ester (PCBM) interfacial degradation on the photovoltaic performance at days 10 (240 h), 20 (480 h), 30 (720 h), and 40 (960 h). The power conversion efficiency increases after the Ag electrode restoration process. While the current density shows a slightly decreased value, the fill factor and open‐circuit voltage increase for the new electrode devices. The decrease in the activation energy due to the restored Ag electrode induces recovery of the fill factor. The diffused I− ions react with the PCBM molecules, resulting in a quasi n‐doping effect of PCBM. Upon electrode exchange, the reversible interaction between the iodine ions and PCBM causes current density variation. The disorder model for the open‐circuit voltage over a wide range of temperatures explains the open‐circuit voltage increase at every electrode exchange. Finally, the degradation mechanism of the inverted perovskite solar cell over 1000 h is described under the proposed recombination system.

Realizing Large-Area Arrays of Semiconducting Fullerene Nanostructures with Direct Laser Interference Patterning.

We present a laser interference patterning method for the facile fabrication of large-area and high-contrast arrays of semiconducting fullerene nanostructures, which does not rely on a tedious application of sacrificial photoresists or photomasks. A solution-deposited phenyl-C61-butyric acid methyl ester (PCBM) fullerene thin film is exposed to a spatially modulated illumination intensity, as realized by a two-beam laser interference. The PCBM molecules exposed to strong intensity are photochemically transformed into a low-solubility dimeric state, so that the nontransformed PCBM molecules can be selectively removed in a subsequent solution-based development step. Following brief exposure to green laser light (λ = 532 nm, t = 5 s, p = 0.17 W cm-2) in the designed two-beam interference setup, and a 1 min development in a tuned acetone-chloroform solution, we realize well-defined and ordered PCBM nanostripe patterns with a fwhm line width of ∼200 nm and a repetition rate of ∼2.900 lines mm-1 over a large area of 1 cm2. We demonstrate that a desired high contrast is effectuated because the initial PCBM-dimer transformation rate is dependent on the square of the illumination intensity. The semiconducting functionality of the patterned fullerene is verified in a field-effect transistor experiment, where a typical PCBM nanostripe featured an electron mobility of 5.3 × 10-3 cm2 V-1 s-1 and an on/off ratio of 3 × 103.

Ultra-Low Powered CNT Synaptic Transistor Utilizing Double PI:PCBM Dielectric Layers

We demonstrated a CNT synaptic transistor by integrating 6,6-phenyl-C61 butyric acid methyl ester(PCBM) molecules as charge storage molecules in a polyimide(PI) dielectric layer with carbon nanotubes(CNTs) for the transistor channel. Specifically, we fabricated and compared three different kinds of CNT-based synaptic transistors: a control device with Al2O3/PI, a single PCBM device with Al2O3/PI:PCBM(0.1 wt%), and a double PCBM device with Al2O3/PI:PCBM(0.1 wt%)/PI:PCBM(0.05 wt%). Statistically, essential device parameters such as Off and On currents, On/Off ratio, device yield, and longterm retention stability for the three kinds of transistor devices were extracted and compared. Notably, the double PCBM device exhibited the most excellent memory transistor behavior. Pulse response properties with postsynaptic dynamic current were also evaluated. Among all of the testing devices, double PCBM device consumed such low power for stand-by and its peak current ratio was so large that the postsynaptic current was also reliably and repeatedly generated. Postsynaptic hole currents through the CNT channel can be generated by electrons trapped in the PCBM molecules and last for a relatively short time(~ hundreds of msec). Under one certain testing configuration, the electrons trapped in the PCBM can also be preserved in a nonvolatile manner for a long-term period. Its integrated platform with extremely low stand-by power should pave a promising road toward next-generation neuromorphic systems, which would emulate the brain power of 20W.

Investigation of the light-soaking effect in organic solar cells using dielectric permittivity and electric modulus approaches

We demonstrate the influence of a light-soaking treatment on current-voltage characteristics, external quantum efficiency and dielectric response of an encapsulated P3HT:PCBM bulk heterojunction inverted organic solar cell. Furthermore, we apply dielectric permittivity and electric modulus approaches to identify relaxation peaks observed in this device. We discuss previously reported explanations of the light-soaking effect on the basis of our experimental results, showing that the light-soaking effect originates from dipole formation at the ZnO/P3HT:PCBM interface. In addition, we find that metal oxide hole and electron selective layers prevent the P3HT:PCBM molecules' reorientations and, thus, enhance its thermal stability. This type of experimental observations are expected to provide new prospective on the fundamental aspect of elementary charge transfer modifications in organic solar cells.

Photogeneration of Charge Carriers in (Phenyl-C61-butyric Acid Methyl Ester) Mixed with a Small Amount of Polymers

Photogeneration of charge carriers in closely packed phenyl-C61-butyric acid methyl ester (PCBM) was investigated by means of the xerographic discharge technique. It was found that the position of the center of mass of the thermalized electron is positioned at a distance that is integral to the multiplicity of the center-to-center distance between the adjacent PCBM molecules. For a low electric field, 104–107 V/m, the most photogenerated electrons originate from the electrons thermalized at the molecule next but one to the geminate recombination center. For the threshold electric field (ca. 2 × 108 V/m) the expected value of the thermalization length, ca. 1.9 nm, is independent of the assumed distribution functions of thermalization distance of the electron–hole pairs. The Coulomb binding energy for this characteristic of PCBM electron–hole separation length is correlated with the threshold energy value separating the extrinsic and intrinsic photogeneration in fullerenes. The model predicts the observed e...

Quantitative Analysis of the Molecular Dynamics of P3HT:PCBM Bulk Heterojunction.

The optoelectronic properties of blends of conjugated polymers and small molecules are likely to be affected by the molecular dynamics of the active layer components. We study the dynamics of regioregular poly(3-hexylthiophene) (P3HT):phenyl-C61-butyric acid methyl ester (PCBM) blends using molecular dynamics (MD) simulation on time scales up to 50 ns and in a temperature range of 250-360 K. First, we compare the MD results with quasi-elastic neutron-scattering (QENS) measurements. Experiment and simulation give evidence of the vitrification of P3HT upon blending and the plasticization of PCBM by P3HT. Second, we reconstruct the QENS signal based on the independent simulations of the three phases constituting the complex microstructure of such blends. Finally, we found that P3HT chains tend to wrap around PCBM molecules in the amorphous mixture of P3HT and PCBM; this molecular interaction between P3HT and PCBM is likely to be responsible for the observed frustration of P3HT, the plasticization of PCBM, and the partial miscibility of P3HT and PCBM.

Fullerene-Containing Electrically Conducting Electron Beam Resist for Ultrahigh Integration of Nanometer Lateral-Scale Organic Electronic Devices

An outstanding issue with organic devices is the difficulty of simultaneously controlling the lateral size and position of structures at submicron or nanometer scales. In this study, nanocomposite electron beam (EB) organic resists are proved to be excellent candidates for electrically conductive and/or memory component materials for submicron or nanometer lateral-scale organic electronic devices. The memory and the resist patterning characteristics are investigated for a positive electron beam resist of ZEP520a containing [6,6]-phenyl-C61 butyric acid methyl ester (PCBM). Regarding the memory characteristics, good programming and excellent retention characteristics are obtained for electrons. The carrier transfer and retention mechanisms are also investigated. Regarding the resist patterning characteristics, it is found that line patterns (square patterns) of ZEP520a containing PCBM can be made with widths (side lengths) of less than 200 nm by using an extremely simple process with only EB exposures and developments. The distribution of PCBM molecules or their aggregations is also clarified in ZEP520a containing PCBM. The results of this study open the door to the simple fabrication of highly integrated flexible memories and electrical wires as well as of single-electron or quantum devices, including quantum information devices and sensitive biosensors for multiplexed and simultaneous diagnoses.

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

Abstract 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.

Strain Modulation of Band Offsets at the PCBM/P3HT Heterointerface

Improving the efficiency of organic solar cells requires atomic insight into the interface electronic band alignment of the donor and acceptor moieties composing the device. In this article, we use ab initio calculations, with inclusion of long-range (van der Waals) interactions, to address the solid-state properties of a bulk heterojunction heterointerface between a single ordered layer of PCBM molecules adsorbed on a clean P3HT crystalline polymer. The studied interface model allowed us to focus on the basic mechanisms responsible for charge polarization and migration at the interface and to refer the energies of both moieties to the same origin. After the accurate evaluation of the relative energy positions of the near-gap electronic levels in the PCBM/P3HT complex and of the optical spectra useful for determining the nature of the electronic states, we analyzed the effect of uniaxial stress on the band alignment, and we found that both the polymer band gap and the offset between the LUMO levels of the...

Morphology Control in Films of Isoindigo Polymers by Side-Chain and Molecular Weight Effects.

The performance of devices relying on organic electronic materials, such as organic field-effect transistors (OFET) and organic photovoltaics (OPV), is strongly correlated to the morphology of the conjugated material in thin films. For instance, several factors such as polymer solubility, weak intermolecular forces between polymers and fullerene derivatives, and film drying time impact phase separation in the active layer of a bulk heterojunction OPV device. In an effort to probe the influence of polymer assembly on morphology of polymer thin films and phase separation with fullerene derivatives, five terthiophene-alt-isoindigo copolymers were synthesized with alkyl side-chains of varying lengths and branching on the terthiophene unit. These P[T3(R)-iI] polymers were designed to have similar optoelectronic properties but different solubilities in o-dichlorobenzene and were predicted to have different tendencies for crystallization. All polymers with linear alkyl chains exhibit similar thin film morphologies as investigated by grazing-incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM). The main differences in electronic and morphological properties arise when P[T3(R)-iI] is substituted with branched 2-ethylhexyl (2EH) side-chains. The bulky 2EH substituents lead to a blue-shifted absorption, a lower ionization potential, and reduced ordering in polymer thin films. The five P[T3-iI] derivatives span hole mobilities from 1.5 × 10-3 to 2.8 × 10-2 cm2 V-1 s-1 in OFET devices. In OPV devices, the 2EH-substituted polymers yield open-circuit voltages of 0.88 V in BHJ devices yet low short-circuit currents of 0.8 mA cm-2, which is explained by the large phase separation observed by AFM in blends of P[T3(2EH)-iI] with PC71BM. In these P[T3(R)-iI] systems, the propensity for the polymers to self-assemble prior to aggregation of PC71BM molecules was key to achieving fine phase separation and increased short-circuit currents, eventually resulting in power conversion efficiencies of 5% in devices processed using a single solvent.

Study of the cold charge transfer state separation at the TQ1/PC71 BM interface.

Charge transfer (CT) state separation is one of the most critical processes in the functioning of an organic solar cell. In this article, we study a bilayer of TQ1 and PC71 BM molecules presenting disorder at the interface, obtained by means of Molecular Dynamics. The study of the CT state splitting can be first analyzed through the CT state splitting diagram, introduced in a previous work. Through this analysis, we identify the possibility of CT state splitting within Marcus Theory in function of the electric field. Once the right range of electric fields has been identified, we perform Kinetic Monte Carlo simulations to estimate percentages and times for the CT state splitting and the free charge carriers collection. Statistical information extracted from these simulations allows us to highlight the importance of polarization and to test the limits of the predictions given by the CT state splitting diagram. © 2017 Wiley Periodicals, Inc.

Analysis and modification of defective surface aggregates on PCDTBT:PCBM solar cell blends using combined Kelvin probe, conductive and bimodal atomic force microscopy.

Organic photovoltaic systems comprising donor polymers and acceptor fullerene derivatives are attractive for inexpensive energy harvesting. Extensive research on polymer solar cells has provided insight into the factors governing device-level efficiency and stability. However, the detailed investigation of nanoscale structures is still challenging. Here we demonstrate the analysis and modification of unidentified surface aggregates. The aggregates are characterized electrically by Kelvin probe force microscopy and conductive atomic force microscopy (C-AFM), whereby the correlation between local electrical potential and current confirms a defective charge transport. Bimodal AFM modification confirms that the aggregates exist on top of the solar cell structure, and is used to remove them and to reveal the underlying active layer. The systematic analysis of the surface aggregates suggests that the structure consists of PCBM molecules.

Annealing-free multi-thermal techniques comprising aging, cycling and seeding to enhance performance of thick P3HT:PCBM photovoltaic cells via developing hairy crystals

Distinct multi-thermal treatments comprising cycling, aging, and seeding were introduced to prepare very thick bulk heterojunction (BHJ) active layers (ca. 800nm) of poly(3-hexylthiophene) (P3HT):phenyl-C71-butyric acid methyl ester (PC71BM) photovoltaic cells. To this end, various P3HT48800-based rod-coil block copolymers having the coily blocks of polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(ethylene glycol) (PEG) were synthesized. The grazing incidence X-ray scattering, field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM) analyses proved that the dielectric coily blocks, which were excluded from the P3HT crystalline structure, accumulated on the crystals surface without decreasing the crystal quality and formed hairy crystals. The multi-thermal techniques facilitated stacking of the growth planes in π-π direction for the P3HT crystals, thereby, this dimension was improved from 5 to 27nm for conventionally prepared BHJs to 53–265nm for multi-thermally developed ones. The hydrophobic coily blocks were capable of neutralizing the influence of the PCBM molecules presence in the growth environment, which resulted in the larger P3HT crystals in a similar condition. By switching the conventional spin coating approach to the cycling, aging, and seeding methods, the P3HT crystals and the PCBM clusters were gradually coarsened and the respective d-spacings decreased. This trend enhanced the hole mobility (=8.8×10−5cm2/Vs), electron mobility (=2.5×10−3cm2/Vs), short circuit current density (Jsc=12.02mA/cm2), fill factor (FF=69%), and power conversion efficiency (PCE=4.39%) up to the maximum values for seeding approach. Moreover, the higher percentages of face-on orientation were detected in the BHJs with lower d-spacings in the hexyl side chain direction. Hairy P3HT48800-b-PS crystals developed by seeding method possessed the highest face-on orientation (~5.5%).

Simultaneously Enhanced Efficiency and Stability of Polymer Solar Cells by Employing Solvent Additive and Upside-down Drying Method.

The morphology of active layer plays an important role in determining the power conversion efficiency (PCE) and stability of polymer solar cells (PSCs), which strongly depend on the dynamic drying process of active layer. In this work, an efficient and universal method was developed to let active layer undergo upside-down drying process in a covered glass Petri dish. For the PSCs based on PTB7-Th:PC71BM, the champion PCEs were improved from 8.58% to 9.64% by mixing 3 vol % 1,8-di-iodooctane and further to 10.30% by employing upside-down drying method. The enhanced PCEs of PSCs with active layers undergoing upside-down drying process are mainly attributed to the optimized vertical phase separation, the more ordered and tightly packed π-π stacking of polymer molecules. Meanwhile, PC71BM molecules can be frozen in more ordered and tightly packed π-π stacking polymer network, which lead to the enhanced stability of PSCs. The universality of upside-down drying method can be solidly confirmed from PSCs with PTB7:PC71BM, PffBT4T-2OD:PC71BM, or PBDT-TS1:PC71BM as active layers, respectively. The molecular packing and phase separation of blend films with different solvent additives and drying methods were investigated by grazing incidence X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy.

Interface modification of CH3NH3PbI3/PCBM by pre-heat treatment for efficiency enhancement of perovskite solar cells

An interfacial modification of CH3NH3PbI3/PCBM is investigated by pre-heating PCBM solution before spin-coating on the CH3NH3PbI3layer.By adjusting PCBM concentration, PCBM films were optimized to form homogeneous films. Besides, the pre-heat treatment of PCBM solution exhibits a better covered area over CH3NH3PbI3 layer with reduced pinhole compared with the non-heat treatment. This can be explained by the higher thermal energy PCBM molecules of the pre-heat solution leading to higher molecule mobility that can reorganizes a structural as well as enhance the diffusion and enhance coverage of PCBM films over CH3NH3PbI3. The optimized cell is enhanced with average power conversion efficiency from 4.59% up to 5.76% (6.44% maximum) by heat treatment. To investigate interface between CH3NH3PbI3 and PCBM, the contact angle was measured and found that the contact angle of PCBM films were higher after heat treatment suggesting re-alignment and better orientation of PCBM on perovskite film. The better orientation of PCBM can be explained in term of hydrophilic/hydrophobic property of the interface between CH3NH3PbI3 and PCBM. These results suggest that pre-heat treatment of PCBM solution has ability to modify the interface for better orientation of PCBM and resulting in efficiency enhancement due to better carrier transport direction at the CH3NH3PbI3/PCBM interfaces for perovskite solar cells. In addition, the better orientation that the head (non-polar)is oriented at outer surface can also prevent the solar cells from surrounding moisture.

Quantitative correlation of the effects of crystallinity and additives on nanomorphology and solar cell performance of isoindigo-based copolymers.

The high power conversion efficiency of bulk heterojunction (BHJ) polymer solar cells can be achieved from either low crystallinity (P3TI) or high crystallinity (P6TI) of isoindigo-based donor-acceptor alternating copolymers blended with PC71BM by controlling nanophase separation using additives. P3TI shows similar device performance regardless of the type of additives, while P6TI is significantly affected by whether the additive is aliphatic or aromatic. To understand the interplays of crystallinity of polymers and the type of additive on the formation of nanomorphology of BHJ, we employed the simultaneous grazing-incidence small- and wide-angle X-ray scattering (GISAXS and GIWAXS) technique to perform the quantitative investigation. By incorporating additives, the PC71BM molecules can be easily intercalated into the P3TI polymer-rich domain and the size of the PC71BM clusters is reduced from about 24 nm to about 5 nm by either aliphatic 1,8-diiodooctane (DIO) or aromatic 1-chloronaphthalene (CN). On comparison, it is found to be more difficult for PC71BM molecules to be intercalated into the highly crystalline P6TI dense domain, and the PC71BM molecules have a higher tendency to be self-aggregated, which results in a larger size of PC71BM clusters of about 58 nm. The clusters can be reduced to about 7 nm by DIO and 13 nm by CN. The presence of crystallites in the P6TI domain can interact with the additive to tailor the crystallization of PC71BM clusters to a size similar to that of P6TI crystallites (∼12 nm) and form a connected network for efficient charge transportation. Thus, the power conversion efficiency of P6TI:PC71BM reaches its maximum of 7.04% using aromatic CN additives. This is a new finding of the effect of crystallinity, which is not observed in the common low crystalline donor-acceptor alternating copolymers such as PTB7. Our results provide a useful guideline to manipulate the desired morphology of BHJ films constructed from alternating copolymer with different crystallinity, which is critical for achieving high power conversion efficiency of solar cells.

A new thiophene-copolymer with side-chain LC mesogen group for efficient BHJ solar cells

The control of structure and morphology of the photoactive blend is a fundamental prerequisite for the obtainment of high efficiency values in bulk heterojunction (BHJ) polymeric solar cells. In fact, the presence of disordered amorphous structures in BHJ cells leads to charge recombination, thus reducing the performance of the final device. A new thiophene copolymer functionalized in the side chain with a liquid crystalline (LC) group, poly{(3-hexylthiophene)-co-3[6-(4-cyanodiphenyloxy)hexyl]thiophene}, has been synthesized in order to induce microphase separation when the conjugated electron donor polymer is mixed with the acceptor PCBM in the photoactive blend. Due to its good solubility in common organic solvents, the LC-copolymer has been fully characterized using spectroscopic, thermal and electronic techniques. The results suggest that, upon suitable annealing procedure, the LC-copolymer spontaneously assembles in a highly ordered structure which favors a nano-dispersed aggregation of the PCBM molecules, thus allowing to achieve a power conversion efficiency near to 6%.

Balancing intermolecular interactions by variation of pendent alkyl chains for high performance organic photovoltaics

Understanding the role of appended alkyl side chains is a key issue to enhance photovoltaic performance because the side chains control molecular solubility, film crystallinity, and morphology. For this purpose, we synthesized three new planar aromatic backbone molecules (Eh-Hex, Eh-Eh and Oct-Eh), where the appended alkyl side chains on the aromatic core unit were either 2-ethylhexyl (Eh) or n-octyl (Oct) and those on the side ends were either Eh or hexyl (Hex). Characterization of the molecular films revealed that all of the molecules were crystalline with mainly edge-on orientation, while the Eh-Hex and Eh-Eh molecules having Eh groups on the core units manifested higher crystallinity than the molecule (Oct-Eh) having Oct groups on the core units. Of the small molecule:PC71BM blend films, only the Eh-Hex case exhibited both good intermolecular packing and uniformly distributed nanoscopic networks of molecular channels, maintaining extensive interfacial contacts between the Eh-Hex and PC71BM domains. On the other hand, the Eh-Eh molecules showed poor miscibility with PC71BM, and the Oct-Eh molecules displayed excessive miscibility with PC71BM. These morphological differences resulted in significant differences in the photovoltaic performance of the devices using small molecule:PC71BM blend films. Inverted-type photovoltaic devices fabricated using the Eh-Hex:PC71BM blend had the highest power conversion efficiency among the three molecule-based devices. Overall, this work demonstrated that both the type of alkyl side chain and its position are crucial factors controlling the balance of interactions between small molecules and PC71BM molecules, which can significantly alter blend morphology and photovoltaic performance.