High‐Performance Air‐Processed Polymer–Fullerene Bulk Heterojunction Solar Cells

High photovoltaic device performance is demonstrated in ambient‐air‐processed bulk heterojunction solar cells having an active blend layer of organic poly(3‐hexylthiophene) (P3HT): [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM), with power conversion efficiencies as high as 4.1%, which is comparable to state‐of‐the‐art bulk heterojunction devices fabricated in air‐free environments. High‐resolution transmission electron microscopy is combined with detailed analysis of electronic carrier transport in order to quantitatively understand the effects of oxygen exposure and different thermal treatments on electronic conduction through the highly nanostructured active blend network. Improvement in photovoltaic device performance by suitable post‐fabrication thermal processing results from the reduced oxygen charge trap density in the active blend layer and is consistent with a corresponding slight increase in thickness of an ～4 nm aluminum oxide hole‐blocking layer present at the electron‐collecting contact interface.     

Self‐Doping Fullerene Electrolyte‐Based Electron Transport Layer for All‐Room‐Temperature‐Processed High‐Performance Flexible Polymer Solar Cells

To achieve high‐performance large‐area flexible polymer solar cells (PSCs), one of the challenges is to develop new interface materials that possess a thermal‐annealing‐free process and thickness‐insensitive photovoltaic properties. Here, an n‐type self‐doping fullerene electrolyte, named PCBB‐3N‐3I, is developed as electron transporting layer (ETL) for the application in PSCs. PCBB‐3N‐3I ETL can be processed at room temperature, and shows excellent orthogonal solvent processability, substantially improved conductivity, and appropriate energy levels. PCBB‐3N‐3I ETL also functions as light‐harvesting acceptor in a bilayer solar cell, contributing to the overall device performance. As a result, the PCBB‐3N‐3I ETL‐based inverted PSCs with a PTB7‐Th:PC₇₁BM photoactive layer demonstrate an enhanced power conversion efficiency (PCE) of 10.62% for rigid and 10.04% for flexible devices. Moreover, the device avoids a thermal annealing process and the photovoltaic properties are insensitive to the thickness of PCBB‐3N‐3I ETL, yielding a PCE of 9.32% for the device with thick PCBB‐3N‐3I ETL (61 nm). To the best of one's knowledge, the above performance yields the highest efficiencies for the flexible PSCs and thick ETL‐based PSCs reported so far. Importantly, the flexible PSCs with PCBB‐3N‐3I ETL also show robust bending durability that could pave the way for the future development of high‐performance flexible solar cells.     

Modular construction of P3HT/PCBM planar-heterojunction solar cells by lamination allows elucidation of processing–structure–function relationships

Contrary to polymer solar cells with bulk-heterojunction active layers, devices with planar-heterojunction active layers allow the decoupling of active layer phase separation from constituent crystallization, and their relative influence on device performance. We fabricated planar-heterojunction devices by first processing the electron donor and electron acceptor in isolation; they were subsequently laminated across the donor–acceptor interface to establish electrical contact. Thermal annealing was intentionally avoided after lamination to maintain the pristine charge transfer interface. Lamination thus obviates the need for solvent orthogonality; more importantly, it provides independent process tuning of individual organic semiconductor layers, ultimately allowing control over constituent structural development. We found the short-circuit current density of planar-heterojunction solar cells comprising poly(3-hexyl thiophene), P3HT, and [6,6]-phenyl-C₆₁-butyric acid methyl ester, PCBM, as the electron donor and acceptor, respectively, to be generally independent of the annealing history of P3HT. On the contrary, thermal annealing PCBM prior to lamination mainly led to a reduction in short-circuit current density. This deterioration is correlated with the development of preferentially oriented PCBM crystals that hinders electron transport in the vertical direction.     

Efficient bulk heterojunction photovoltaic devices based on diketopyrrolopyrrole containing small molecule as donor and modified PCBM derivatives as electron acceptors

A new solution processable small molecule (DPP-CN) containing electron donor diketopyrrolopyrrole (DPP) core and cyanovinylene 4-nitrophenyl (CN) electron acceptor has synthesized for use as the donor material in the bulk heterojunction organic solar cells along with PCBM, modified PCBM i.e. F and A as electron acceptor. It showed a broad absorption in longer wavelength region having optical band gap around 1.64 eV. We have used PCBM, F and A as electron acceptor for the fabrication of bulk heterojunction photovoltaic devices. The power conversion efficiency (PCE) of the BHJ devices based on DPP-CN:PCBM, DPP-CN:F and DPP-CN:A blends cast from the THF solvent is 1.83%, 2.79% and 2.83%, respectively. The increase in the PCE based on F and A as electron acceptor is mainly due to the increase in both short circuit current (J_sc) and open circuit voltage (V_oc). The PCE value of the photovoltaic devices based on the blends DPP-CN:PCBM, DPP-CN:F and DDP-CN:A cast from the mixed solvents (DIO/THF) has been further improved up to 2.40%, 3.32% and 3.34%, respectively. This improvement is mainly due to the increased value of J_sc, which is attributed not only to the increase of crystallinity, but also to the morphological change in the film cast from mixed solvent. Finally, the device ITO/PEDOT:PSS/DPP-CN:A (DIO/THF cast)/TiO₂/Al device shows a PCE of 3.9%. The improved device performance could be attributed to the electron transporting and hole-blocking capabilities due to the introduced TiO₂ buffer layer.     

Charge selectivity in polymer:Fullerene-based organic solar cells with a chemically linked polyethylenimine interlayer

The power conversion efficiency of solar cells can be optimized via an efficient charge collection by electrodes. In this study, a simple linear polyethylenimine (LPEI), which is an insulating polymer, was adopted as the cathode interfacial layer of poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM)-based bulk-heterojunction organic solar cells (OSCs) with a non-inverted configuration. All photovoltaic parameters of the OSCs were significantly enhanced by depositing LPEI onto the oxygen plasma-treated P3HT:PCBM active layers. The causes of performance enhancement in OSCs were studied. Results revealed that the microstructure and morphology of the P3HT:PCBM layer were almost unaffected by the oxygen plasma treatment and the subsequent LPEI deposition. The X-ray photoelectron spectra of the specimens demonstrated that with the aid of oxygen plasma treatment, the linked LPEI molecules formed a well-aligned dipole layer on top of the P3HT:PCBM layer through the bonding of nitrogen (N) with oxygen (O). The results from quantum chemical calculations showed that the LPEI molecule with an N–O bond had a larger dipole moment at an appropriate direction than that without an N–O bond. By contrast, the LPEI molecules can form a dipole layer with a random orientation in the absence of N–O bonds. The conductive atomic force microscopy images of the specimens showed that the well-aligned dipole layer could facilitate electron transfer and could block hole transfer from the P3HT:PCBM to the cathodes. The well-aligned and augmented interface dipoles improved the charge selectivity at the cathodes and the photovoltaic performance of the devices.     

The Relation Between Open‐Circuit Voltage and the Onset of Photocurrent Generation by Charge‐Transfer Absorption in Polymer : Fullerene Bulk Heterojunction Solar Cells

Photocurrent generation by charge‐transfer (CT) absorption is detected in a range of conjugated polymer–[6,6]‐phenyl C₆₁ butyric acid methyl ester (PCBM) based solar cells. The low intensity CT absorption bands are observed using a highly sensitive measurement of the external quantum efficiency (EQE) spectrum by means of Fourier‐transform photocurrent spectroscopy (FTPS). The presence of these CT bands implies the formation of weak ground‐state charge‐transfer complexes in the studied polymer–fullerene blends. The effective band gap (E_g) of the material blends used in these photovoltaic devices is determined from the energetic onset of the photocurrent generated by CT absorption. It is shown that for all devices, under various preparation conditions, the open‐circuit voltage (V_oc) scales linearly with E_g. The redshift of the CT band upon thermal annealing of regioregular poly(3‐hexylthiophene):PCBM and thermal aging of poly(phenylenevinylene)(PPV):PCBM photovoltaic devices correlates with the observed drop in open‐circuit voltage of high‐temperature treated versus untreated devices. Increasing the weight fraction of PCBM also results in a redshift of E_g, proportional with the observed changes in V_oc for different PPV:PCBM ratios. As E_g corresponds with the effective bandgap of the material blends, a measurement of the EQE spectrum by FTPS allows us to measure this energy directly on photovoltaic devices, and makes it a valuable technique in the study of organic bulk heterojunction solar cells.     

Relating the Morphology of Poly(p‐phenylene vinylene)/Methanofullerene Blends to Solar‐Cell Performance

The performance of bulk‐heterojunction solar cells based on a phase‐separated mixture of donor and acceptor materials is known to be critically dependent on the morphology of the active layer. Here we use a combination of techniques to resolve the morphology of spin cast films of poly(p‐phenylene vinylene)/methanofullerene blends in three dimensions on a nanometer scale and relate the results to the performance of the corresponding solar cells. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and depth profiling using dynamic time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) clearly show that for the two materials used in this study, 1‐(3‐methoxycarbonyl)propyl‐1‐phenyl‐[6,6]‐methanofullerene (PCBM) and poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV), phase separation is not observed up to 50 wt.‐% PCBM. Nanoscale phase separation throughout the film sets in for concentrations of more than 67 wt.‐% PCBM, to give domains of rather pure PCBM in a homogenous matrix of 50:50 wt.‐% MDMO‐PPV/PCBM. Electrical characterization, under illumination and in the dark, of the corresponding photovoltaic devices revealed a strong increase of power conversion efficiency when the phase‐separated network develops, with a sharp increase of the photocurrent and fill factor between 50 and 67 wt.‐% PCBM. As the phase separation sets in, enhanced electron transport and a reduction of bimolecular charge recombination provide the conditions for improved performance. The results are interpreted in terms of a model that proposes a hierarchical build up of two cooperative interpenetrating networks at different length scales.     

Comparison of the Operation of Polymer/Fullerene,Polymer/Polymer,and Polymer/Nanocrystal Solar Cells: A Transient Photocurrent and Photovoltage Study

We utilize transient techniques to directly compare the operation of polymer/fullerene, polymer/nanocrystal, and polymer/polymer bulk heterojunction solar cells. For all devices, poly(3‐hexylthiophene) (P3HT) is used as the electron donating polymer, in combination with either the fullerene derivative phenyl‐C₆₁‐butyric acid methyl ester (PCBM) in polymer/fullerene cells, CdSe nanoparticles in polymer/nanocrystal cells, or the polyfluorene copolymer poly((9,9‐dioctylfluorene)‐2,7‐diyl‐alt‐[4,7‐bis(3‐hexylthien‐5‐yl)‐2,1,3‐benzothiadiazole]‐2,2‐diyl) (F8TBT) in polymer/polymer cells. Transient photocurrent and photovoltage measurements are used to probe the dynamics of charge‐separated carriers, with vastly different dynamic behavior observed for polymer/fullerene, polymer/polymer, and polymer/nanocrystal devices on the microsecond to millisecond timescale. Furthermore, by employing transient photocurrent analysis with different applied voltages we are also able to probe the dynamics behavior of these cells from short circuit to open circuit. P3HT/F8TBT and P3HT/CdSe devices are characterized by poor charge extraction of the long‐lived carriers attributed to charge trapping. P3HT/PCBM devices, in contrast, show relatively trap‐free operation with the variation in the photocurrent decay kinetics with applied bias at low intensity, consistent with the drift of free charges under a uniform electric field. Under solar conditions at the maximum power point, we see direct evidence of bimolecular recombination in the P3HT/PCBM device competing with charge extraction. Transient photovoltage measurements reveal that, at open circuit, photogenerated charges have similar lifetimes in all device types, and hence, the extraction of these long‐lived charges is a limiting process in polymer/nanocrystal and polymer/polymer devices.     

Quantifying Interfacial Electric Fields and Local Crystallinity in Polymer–Fullerene Bulk‐Heterojunction Solar Cells

The challenges of experimentally probing the physical and electronic structures of the highly intermixed organic semiconductor blends that comprise active layers in high‐performance organic photovoltaic (OPV) cells ultimately limit the fundamental understanding of the device performance. We use Fourier‐transform IR (FTIR)‐absorption spectroscopy to quantitatively determine the interfacial electric field in blended poly(3‐hexylthiophene) (P3HT):phenyl‐ C61‐butyric acid methyl ester (PCBM) thin films. The interfacial electric field is ≈0.2 V nm^?1 in the as‐spun film and blends annealing at temperatures as high as 150 °C, which is the optimal annealing temperature in terms of OPV performance. The field decreases to a negligible value upon further annealing to 170 °C, at which temperature PCBM changes from amorphous to crystalline and the open‐circuit voltage of the solar cell decreases from 0.62 to 0.4 V. In addition, our measurements also allow determination of the absolute degree of crystallinity within the acceptor material. The roles of interfacial field and local crystallinity in OPV device performance are discussed.     

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.     

A New Donor–Acceptor–Donor Polyfluorene Copolymer with Balanced Electron and Hole Mobility

A new alternating polyfluorene copolymer poly[2,7‐(9,9‐dioctylfluoren)‐alt‐5,5‐(5′,8′‐di‐2‐thienyl‐(2′,3′‐bis‐(3′′‐octyloxyphenyl)‐quinoxaline))] (APFO‐15), which has electron donor–acceptor–donor units in between the fluorene units, is synthesized and characterized. This polymer has a strong absorption and emission in the visible range of the solar spectrum. Its electroluminescence and photoluminescence emissions extend from about 560 to 900 nm. Moreover, solar cells with efficiencies in excess of 3.5 % have been realized from blends of APFO‐15 and an electron acceptor molecule, a methanofullerene [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM). It has also been observed that electron and hole transport is balanced both in the pure polymer phase and in polymer/PCBM bulk heterojunction films, which makes this material quite attractive for applications in opto‐electronic devices.     

Fullerene‐Free Polymer Solar Cells with Open‐Circuit Voltage above 1.2 V: Tuning Phase Separation Behavior with Oligomer to Replace Polymer Acceptor

This study has proposed to use a well‐defined oligomer F4TBT4 to replace its analogue polymer as electron acceptor toward tuning the phase separation behavior and enhancing the photovoltaic performance of all‐polymer solar cells. It has been disclosed that the oligomer acceptor favors to construct pure and large‐scale phase separation in the polymer:oligomer blend film in contrast to the polymer:polymer blend film. This gets benefit from the well‐defined structure and short rigid conformation of the oligomer that endows it aggregation capability and avoids possible entanglement with the polymer donor chains. The charge recombination is to some extent suppressed and charge extraction is also improved. Finally, the P3HT:F4TBT4 solar cells not only output a high V_OC above 1.2 V, but also achieve a power conversion efficiency of 4.12%, which is two times higher than the P3HT:PFTBT solar cells and is comparable to the P3HT:PCBM solar cells. The strategy of constructing optimum phase separation with oligomer to replace polymer opens up new prospect for the further improvement of the all‐polymer solar cells.     

Materials‐Scale Implications of Solvent and Temperature on [6,6]‐Phenyl‐C61‐butyric Acid Methyl Ester (PCBM): A Theoretical Perspective

The ability to detail how molecules pack in the bulk and at the various materials interfaces in the active layer of an organic solar cell is important to further understanding overall device performance. Here, [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM), a preferred electron‐acceptor material in organic solar cells, is studied through molecular dynamics (MD) simulations; the goal is to examine the effects of temperature and trace solvents on the packing and morphological features of bulk PCBM. Solubility (miscibility) parameters, melting and order‐disorder transitions, surface energies, and orientational distributions as a function of different starting configurations are discussed. On the basis of the derived morphologies, electronic structure calculations and a kinetic Monte Carlo approach are combined to evaluate the parameters impacting electron mobility in crystalline and amorphous PCBM structures.     

Improving the fill factor of N2200-based all polymer solar cells by introducing EPPDI as a solid additive

A cheap and commercially available small molecule (namely EPPDI) is introduced to the active layer of N2200-based all polymer solar cells as a solid additive. EPPDI at the optimal ratio can improve the D-A nano-scale morphology and reduce trap density of the active layer by filling morphological spaces. As a result, the photovoltaic performance of the resulting devices based on PF2:N2200 are increased from 6.28% to 7.03% with significantly enhanced fill factor. This work demonstrates a facile approach for improving the performance of all polymer solar cells.     

Alkoxy‐Functionalized Thienyl‐Vinylene Polymers for Field‐Effect Transistors and All‐Polymer Solar Cells

π‐conjugated polymers based on the electron‐neutral alkoxy‐functionalized thienyl‐vinylene (TVTOEt) building‐block co‐polymerized, with either BDT (benzodithiophene) or T2 (dithiophene) donor blocks, or NDI (naphthalenediimide) as an acceptor block, are synthesized and characterized. The effect of BDT and NDI substituents (alkyl vs alkoxy or linear vs branched) on the polymer performance in organic thin film transistors (OTFTs) and all‐polymer organic photovoltaic (OPV) cells is reported. Co‐monomer selection and backbone functionalization substantially modifies the polymer MO energies, thin film morphology, and charge transport properties, as indicated by electrochemistry, optical spectroscopy, X‐ray diffraction, AFM, DFT calculations, and TFT response. When polymer P7 is used as an OPV acceptor with PTB7 as a donor, the corresponding blend yields TFTs with ambipolar mobilities of μ_e = 5.1 × 10^?3 cm² V^–1 s^–1 and μ_h = 3.9 × 10^?3 cm² V^–1 s^–1 in ambient, among the highest mobilities reported to date for all‐polymer bulk heterojunction TFTs, and all‐polymer solar cells with a power conversion efficiency (PCE) of 1.70%, the highest reported PCE to date for an NDI‐polymer acceptor system. The stable transport characteristics in ambient and promising solar cell performance make NDI‐type materials promising acceptors for all‐polymer solar cell applications.     

Trap‐Assisted Recombination via Integer Charge Transfer States in Organic Bulk Heterojunction Photovoltaics

Organic photovoltaics are under intense development and significant focus has been placed on tuning the donor ionization potential and acceptor electron affinity to optimize open circuit voltage. Here, it is shown that for a series of regioregular‐poly(3‐hexylthiophene):fullerene bulk heterojunction (BHJ) organic photovoltaic devices with pinned electrodes, integer charge transfer states present in the dark and created as a consequence of Fermi level equilibrium at BHJ have a profound effect on open circuit voltage. The integer charge transfer state formation causes vacuum level misalignment that yields a roughly constant effective donor ionization potential to acceptor electron affinity energy difference at the donor–acceptor interface, even though there is a large variation in electron affinity for the fullerene series. The large variation in open circuit voltage for the corresponding device series instead is found to be a consequence of trap‐assisted recombination via integer charge transfer states. Based on the results, novel design rules for optimizing open circuit voltage and performance of organic bulk heterojunction solar cells are proposed.     

Successive Spray Deposition of P3HT/PCBM Organic Photoactive Layers: Material Composition and Device Characteristics

Controlling the active layer composition in organic electronic devices represents one of the major challenges in their fabrication. In particular, the composition of mixed donor/acceptor active layers for photosensitive device applications is known to strongly influence device performance. Here, an alternative approach for the preparation of organic heterojunction photoactive layers by successive spray deposition of the donor material, poly(3‐hexylthiophene) (P3HT), and acceptor material, [6,6]‐phenyl C61‐butyric acid methyl ester (PCBM), is reported. Optical absorption spectra, X‐ray reflectivity, and cross‐sectional transmission electron microscopy investigations are used to indicate the penetration of PCBM into a previously deposited P3HT layer and the spontaneous formation of a bulk heterojunction (BHJ) within the active layer, which provides the large interfacial area needed for efficient exciton dissociation. It is shown that organic photodiodes composed of photoactive layers prepared using this fabrication method exhibit a performance comparable to conventional BHJ devices in which the active layer is rigorously blended in advance. Moreover, separate handling of the individual materials and their deposition from distinct solutions enables an enhanced control of the active layer composition and hence increases the ability of tuning device characteristics.     

Optical,Electrical, and Magnetic Studies of Organic Solar Cells Based on Low Bandgap Copolymer with Spin ½ Radical Additives

The charge photogeneration and recombination processes in organic photovoltaic solar cells based on blend of the low bandgap copolymer, PTB7 (fluorinated poly‐thienothiophene‐benzodithiophene) with C60‐PCBM using optical, electrical, and magnetic measurements in thin films and devices is studied. A variety of steady state optical and magneto‐optical techniques were employed, such as photoinduced absorption (PA), magneto‐PA, doping‐induced absorption, and PA‐detected magnetic resonance (PADMR); as well as picosecond time‐resolved PA. The charge polarons and triplet exciton dynamics in films of pristine PTB7, PTB7/fullerene donor–acceptor (D–A) blend is followed. It is found that a major loss mechanism that limits the power conversion efficiency (PCE) of PTB7‐based solar cell devices is the “back reaction” that leads to triplet exciton formation in the polymer donor from the photogenerated charge‐transfer excitons at the D–A interfaces. A method of suppressing this “back reaction” by adding spin½ radicals Galvinoxyl to the D–A blend is presented; this enhances the cell PCE by ≈30%. The same method is not effective for cells based on PTB7/C70‐PCBM blend, where high PCE is reached even without Galvinoxyl radical additives.     

Bithienopyrroledione‐Based Copolymers,Versatile Semiconductors for Balanced Ambipolar Thin‐Film Transistors and Organic Solar Cells with V oc > 1 V

Conjugated polymer semiconductors P1 and P2 with bithienopyrroledione (bi‐TPD) as acceptor unit are synthesized. Their transistor and photovoltaic performances are investigated. Both polymers display high and balanced ambipolar transport behaviors in thin‐film transistors. P1‐ based devices show an electron mobility of 1.02 cm² V^?1 s^?1 and a hole mobility of 0.33 cm² V^?1 s^?1, one of the highest performance reported for ambipolar polymer transistors. The electron and hole mobilities of P2 transistors are 0.36 and 0.16 cm² V^?1 s^?1, respectively. The solar cells with PC₇₁BM as the electron acceptor and P1/P2 as the donor exhibit a high V _oc about 1.0 V, and a power conversion efficiency of 6.46% is observed for P1‐ based devices without any additives and/or post treatment. The high performance of P1 and P2 is attributed to their crystalline films and short π–π stacking distance (<3.5 Å). These results demonstrate (1) bi‐TPD is an excellent versatile electron‐deficient unit for polymer semiconductors and (2) bi‐TPD‐based polymer semiconductors have potential applications in organic transistors and organic solar cells.