Acceptor-rich bulk heterojunction polymer solar cells with balanced charge mobilities

In this work, we reported efficient polymer solar cells with balanced hole/electron mobilities tuned by the acceptor content in bulk heterojunction blend films. The photovoltaic cells were fabricated with two new wide band-gap D-A polymers PBDDIDT and PBDDIDTT as the donor material. The molecular conformations of new polymers are carefully evaluated by theoretical calculations. The results of photovoltaic studies show that two devices reach their optimal conditions with rich PC₇₁BM content up to 80% in blend films, which is uncommon with most of reported PSCs. The as-cast devices based on PBDDIDT and PBDDIDTT reveal good photovoltaic performance with PCE of 7.04% and 6.40%, respectively. The influence of PC₇₁BM content on photovoltaic properties is further detailed studied by photoluminescence emission spectra, charge mobilities and heterojunction morphology. The results exhibit that more efficient charge transport between donor and acceptor occurs in rich PC₇₁BM blend films. Meanwhile, the hole and electron mobilities are simultaneously enhanced and afford a good balance in rich PC₇₁BM blend films (D/A, 1:4) which is critical for the improvement of current density and fill factors.     

The Effect of Nanoparticle Shape on the Photocarrier Dynamics and Photovoltaic Device Performance of Poly(3‐hexylthiophene):CdSe Nanoparticle Bulk Heterojunction Solar Cells

The charge separation and transport dynamics in CdSe nanoparticle:poly(3‐hexylthiophene) (P3HT) blends are reported as a function of the shape of the CdSe‐nanoparticle electron acceptor (dot, rod, and tetrapod). For optimization of organic photovoltaic device performance it is crucial to understand the role of various nanostructures in the generation and transport of charge carriers. The sample processing conditions are carefully controlled to eliminate any processing‐related effects on the carrier generation and on device performance with the aim of keeping the conjugated polymer phase constant and only varying the shape of the inorganic nanoparticle acceptor phase. The electrodeless, flash photolysis time‐resolved microwave conductivity (FP‐TRMC) technique is used and the results are compared to the efficiency of photovoltaic devices that incorporate the same active layer. It is observed that in nanorods and tetrapods blended with P3HT, the high aspect ratios provide a pathway for the electrons to move away from the dissociation site even in the absence of an applied electric field, resulting in enhanced carrier lifetimes that correlate to increased efficiencies in devices. The processing conditions that yield optimum performance in high aspect ratio CdSe nanoparticles blended with P3HT result in poorly performing quantum dot CdSe:P3HT devices, indicating that the latter devices are inherently limited by the absence of the dimensionality that allows for efficient, prolonged charge separation at the polymer:CdSe interface.     

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.     

Fluorinated and non-fluorinated conjugated polymers showing different photovoltaic properties in polymer solar cells with PFNBr interlayers

Photovoltaic properties of the two polymers (named as PBQ-0F and PBQ-4F) were investigated by employing [6, 6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) as the acceptor and a water-alcohol-soluble polymer interlayer material (named as PFNBr) to fabricate photovoltaic devices. For the PBQ-0F:PC₇₁BM blend, the device using Ca/Al as cathode showed very similar efficiency as the device using PFNBr/Al as cathode, while for the PBQ-0F:PC₇₁BM blend, photovoltaic performance of the device can be distinctly improved by replacing Ca/Al with PFNBr/Al. As a result, the best PCE of the PBQ-4F:PC₇₁BM based devices reached 9.04%, which is much higher than that of the PBQ-0F:PC₇₁BM based devices. The results obtained from the quantum chemistry calculations and water contact angle measurements demonstrate that these two polymers are low polar materials, and also the films based on them have hydrophobic surfaces. Since PFNBr has an amphipathic structure (hydrophobic backbone and hydrophilic side chain) and the blend films of PBQ-4F:PC₇₁BM and PBQ-4F:PC₇₁BM have different surface energies, the PFNBr organization atop these two blend types of should be different, which will affect device photovoltaic performance.     

Lateral Phase Separation Gradients in Spin‐Coated Thin Films of High‐Performance Polymer:Fullerene Photovoltaic Blends

In this study, it is demonstrated that a finer nanostructure produced under a rapid rate of solvent removal significantly improves charge separation in a high‐performance polymer:fullerene bulk‐heterojunction blend. During spin‐coating, variations in solvent evaporation rate give rise to lateral phase separation gradients with the degree of coarseness decreasing away from the center of rotation. As a result, across spin‐coated thin films the photocurrent at the first interference maximum varies as much as 25%, which is much larger than any optical effect. This is investigated by combining information on the surface morphology of the active layer imaged by atomic force microscopy, the 3D nanostructure imaged by electron tomography, film formation during the spin coating process imaged by optical interference and photocurrent generation distribution in devices imaged by a scanning light pulse technique. The observation that the nanostructure of organic photovoltaic blends can strongly vary across spin‐coated thin films will aid the design of solvent mixtures suitable for high molecular‐weight polymers and of coating techniques amenable to large area processing.     

Ternary organic solar cells with improved efficiency and stability enabled by compatible dual-acceptor strategy

To further elevate the power conversion efficiency (PCE) of organic solar cells (OSCs), ternary strategy is one of the most efficient methods via simply incorporating a suitable third component. Here, a nonfullerene small molecule acceptor MOITIC was incorporated into the state-of-art PM6:Y6 binary system to further enhance the photovoltaic performance. Detailed investigation revealed that MOITIC exhibited a good miscibility and compatibility with Y6, forming alloy-like acceptors in the ternary blends. The alloy-like phase promoted the phase separation and optimized the morphology of ternary blend, which afforded higher and more balanced carrier mobility and reduced charge recombination in devices. Moreover, the larger energy offset between PM6 and MOITIC:Y6 acceptor alloy is beneficial to enhance open-circuit voltage (V_oc) of corresponding devices. As a consequence, the optimized ternary OSC (PM6:Y6:MOITIC = 1:1:0.1) showed a significantly increased PCE of 17.1% with simultaneously enhanced V_oc of 0.882 V, short-circuit current density (J_sc) of 25.6 mA cm⁻², and fill factor (FF) of 75.7%, which has about 9% enhancement compared to the control binary PM6:Y6 (15.7%). In addition, the optimized ternary device exhibited better stability. This work indicates that ternary strategy via combining two compatible small molecule acceptors is effective to simultaneously improve the efficiency and stability of OSCs.     

Efficient ternary organic solar cells based on immiscible blends

Organic photovoltaic cells based on ternary blends of materials with complementary properties represent an approach to improve the photon-absorption and/or charge transport within the devices. However, the more complex nature of the ternary system, i.e. in diversity of materials' properties and morphological features, complicates the understanding of the processes behind such optimizations. Here, organic photovoltaic cells with wider absorption spectrum composed of two electron-donor polymers, F8T2, poly(9,9-dioctylfluorene-alt-bithiophene), and PTB7, poly([4,8-bis[(2′-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2′-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]), mixed with [6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM) are investigated. We demonstrate an improvement of 25% in power conversion efficiency in comparison with the most efficient binary blend control devices. The active layers of these ternary cells exhibit gross phase separation, as determined by Atomic Force Microscopy (AFM) and Synchrotron-based Scanning Transmission X-ray Microscopy (STXM).     

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

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

CuPc/C60 bulk heterojunction photovoltaic cells with evidence of phase segregation

This work presents organic photovoltaic (OPV) device study based on cupper phthalocyanine (CuPc) and fullerene (C60) bulk heterojunction (BHJ) structure. By varying blend composition, the optimized performances were obtained in 75%-CuPc containing devices with anode buffer of either CuPc or HPCzI (1,3,4,5,6,7-hexaphenyl-2-{3′-(9-ethylcarbazolyl)}-isoindole). It was discovered by scanning electron microscopy that 75%-CuPc containing film possessed phase separation, which is beneficial to charge transport via percolation process. Additionally, electronic absorption measurement and hole only device study showed that, depending on the mixing ratio, the absorption and the hole transport ability were different. The blend film containing 75% CuPc had the largest integrated absorption with the most CuPc dimmer aggregate and the least C60 aggregate. Moreover, the 75% CuPc blend film also possessed the highest hole transport ability. Thus, the best performance of the 75% CuPc BHJ device is mainly attributed to its good carrier transport originating from phase segregation. The present work highlights the phase separation in CuPc:C60 mixing film with optimized ratio, as well as its corresponding electronic absorption and carrier transport properties, which are essential for OPV device performance. Hence, insights are inferred for further engineering of BHJ OPV devices based on small molecules.     

High performance organic solar cells enabled by an iodinated additive

Additive engineering is a simple and effective strategy to enhance the efficiency of organic solar cells (OSCs). However, traditional additives such as 1,8-diiodooctane (DIO) or 1-chloronaphthalene (CN), suffer from inferior stability, concentration sensitivity, and need additional thermal treatments, which are not desirable for industrial application. Here we introduce a simple, effective and versatile solid additive 1,3-diiodobenzene (1,3-DIB) into the OSCs. In comparison to the control devices, the 1,3-DIB treated OSCs exhibit significantly improved performance with a power conversion efficiency (PCE) of 16.90% for polymer OSCs and a PCE of 14.35% for binary all-small-molecule OSCs. Mechanism studies reveal that 1,3-DIB can improve charge transport and extraction, decrease charge recombination, enhance crystallinity and improve the phase separation. Furthermore, no thermal annealing is needed in PM6:Y6 based OSCs and the 1,3-DIB treated devices show excellent stability and reproducibility in both polymer and small molecule OSCs. Our results demonstrated that additive engineering is a powerful method to enhance the OSC performance.     

Diindenoperylene derivatives: A model to investigate the path from molecular structure via morphology to solar cell performance

Efficient organic electronic devices require a detailed understanding of the relation between molecular structure, thin film growth, and device performance, which is only partially understood at present. Here, we show that small changes in molecular structure of a donor absorber material lead to significant changes in the intermolecular arrangement within organic solar cells. For this purpose, phenyl rings and propyl side chains are fused to the diindenoperylene (DIP) molecule. Grazing incidence X-ray diffraction and variable angle spectroscopic ellipsometry turned out to be a powerful combination to gain detailed information about the thin film growth. Planar and bulk heterojunction solar cells with C60 as acceptor and the DIP derivatives as donor are fabricated to investigate the influence of film morphology on the device performance. Due to its planar structure, DIP is found to be highly crystalline in pristine and DIP:C60 blend films while its derivatives grow liquid-like crystalline. This indicates that the molecular arrangement is strongly disturbed by the steric hindrance induced by the phenyl rings. The high fill factor (FF) of more than 75% in planar heterojunction solar cells of the DIP derivatives indicates excellent charge transport in the pristine liquid-like crystalline absorber layers. However, bulk heterojunctions of these materials surprisingly result in a low FF of only 54% caused by a weak phase separation and thus poor charge carrier percolation paths due to the lower ordered thin film growth. In contrast, crystalline DIP:C60 heterojunctions lead to high FF of up to 65% as the crystalline growth induces better percolation for the charge carriers. However, the major drawback of this crystalline growth mode is the nearly upright standing orientation of the DIP molecules in both pristine and blend films. This arrangement results in low absorption and thus a photocurrent which is significantly lower than in the DIP derivative devices, where the liquid-like crystalline growth leads to a more horizontal molecular alignment. Our results underline the complexity of the molecular structure-device performance relation in organic semiconductor devices.     

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.     

High Fill Factor and Open Circuit Voltage in Organic Photovoltaic Cells with Diindenoperylene as Donor Material

Small‐molecule photovoltaic cells using diindenoperylene (DIP) as a new donor material in combination with the fullerene C₆₀ as an electron acceptor are demonstrated. In addition to the successful application in planar and bulk heterojunction devices, a comprehensive analysis including structural studies, the determination of the energy level alignment and electrical transport investigations is given, stressing the correlation between growth conditions, film morphology, and device performance. Due to pronounced crystallinity and a large surface area of DIP films grown at elevated temperature, exceptionally high fill factors of almost 75% are achieved in planar heterojunction cells. Bulk heterojunctions exhibit large‐scale phase separation forming a bicontinuous network of both molecular species, which enables efficient exciton dissociation and charge carrier transport. The high ionization potential of DIP and the favorable energy level alignment with the fullerene C₆₀ yield large open circuit voltages close to 1 V and comparable power conversion efficiencies of about 4% in both cell architectures.     

Efficient bilayer heterojunction polymer solar cells with bumpy donor–acceptor interface formed by facile polymer blend

We demonstrated a facile method for the fabrication of bilayer polymer solar cells with a controlled heterojunction structure via simple polymer blends. The spontaneous phase separation of poly(3-hexylthiophene)/polyethylene glycol blends provides a bumpy electron-donor layer with characteristic circular depressions. The diameter and depth of the circular depressions can be controlled by varying the PEG content of the blend. The deposition of -phenyl-C61-butyric acid methyl ester as an electron-acceptor layer then creates an interpenetrating donor–acceptor interface for bilayer heterojunction polymer solar cells. The bumpy morphology of the interface results in a significant enhancement in the power conversion efficiency over that of the bilayer polymer solar cells with a typical planar interface, which is mainly due to an increase of photocurrent. An estimation of the field-dependent possibility of charge separation indicates that charge extraction is more efficient than charge recombination in the bilayer devices and the increase in the interfacial area of solar cells with a bumpy-interface leads to generate more electron-hole pairs at the interface.     

Laminated Organic Photovoltaic Modules for Agrivoltaics and Beyond: An Outdoor Stability Study of All-Polymer and Polymer:Small Molecule Blends

The integration of organic photovoltaic (OPV) modules on greenhouses is an encouraging practice to offset the energy demands of crop growth and provide extra functionality to dedicated farmland. Nevertheless, such OPV devices must meet certain optical and stability requirements to turn net zero energy greenhouse systems a reality. Here a donor:acceptor polymer blend is optimized for its use in laminated devices while matching the optical needs of crops. Optical modeling is performed and a greenhouse figure-of-merit is introduced to benchmark the trade-off between photovoltaic performance and transparency for both chloroplasts and humans. Balanced donor:acceptor ratios result in better-performing and more thermally stable devices than acceptor-enriched counterparts. The optimized polymer blend and state-of-the-art polymer:small-molecule blends are next transferred to 25 cm² laminated modules processed entirely from solution and in ambient conditions. The modules are mounted on a greenhouse as standalone or 4-terminal tandem configurations and their outdoor stability is tracked for months. The study reveals degradation modes undetectable under laboratory conditions such as module delamination, which accounts for 10–20% loss in active area. Among the active layers tested, polymer:fullerene blends are the most stable and position as robust light harvesters in future building-integrated OPV systems.     

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.     

The Effect of Poly(3‐hexylthiophene) Molecular Weight on Charge Transport and the Performance of Polymer:Fullerene Solar Cells

The time‐of‐flight method has been used to study the effect of P3HT molecular weight (M_n = 13–121 kDa) on charge mobility in pristine and PCBM blend films using highly regioregular P3HT. Hole mobility was observed to remain constant at 10^?4 cm²V^?1s^?1 as molecular weight was increased from 13–18 kDa, but then decreased by one order of magnitude as molecular weight was further increased from 34–121 kDa. The decrease in charge mobility observed in blend films is accompanied by a change in surface morphology, and leads to a decrease in the performance of photovoltaic devices made from these blend films.     

Efficient Polythiophene/Polyfluorene Copolymer Bulk Heterojunction Photovoltaic Devices: Device Physics and Annealing Effects

Here the influence of annealing on the operational efficiency of all‐polymer solar cells based on blends of the polymers poly(3‐hexylthiophene) (P3HT) and poly((9,9‐dioctylfluorene)‐2,7‐diyl‐alt‐[4,7‐bis(3‐hexylthiophen‐5‐yl)‐2,1,3‐benzothiadiazole]‐2′,2″‐diyl) (F8TBT) is investigated. Annealing of completed devices is found to result in an increase in power conversion efficiency from 0.14 to 1.20%, while annealing of films prior to top electrode deposition increases device efficiency to only 0.19% due to a lowering of the open‐circuit voltage and short‐circuit current. By studying the dependence of photocurrent on intensity and effective applied bias, annealing is found to increase charge generation efficiency through an increase in the efficiency of the separation of bound electron‐hole pairs following charge transfer. However, unlike many other all‐polymer blends, this increase in charge separation efficiency is not only due to an increase in the degree of phase separation that assists in the spatial separation of electron‐hole pairs, but also due to an order of magnitude increase in the hole mobility of the P3HT phase. The increase in hole mobility with annealing is attributed to the ordering of P3HT chains evidenced by the red‐shifting of P3HT optical absorption in the blend. We also use X‐ray photoelectron spectroscopy (XPS) to study the influence of annealing protocol on film interface composition. Surprisingly both top and bottom electrode/blend interfaces are enriched with P3HT, with the blend/top electrode interface consisting of more than 95% P3HT for as‐spun films and films annealed without a top electrode. Films annealed following top electrode deposition, however, show an increase in F8TBT composition to ～15%. The implications of interfacial composition and the origin of open‐circuit voltage in these devices are also discussed.     

Anthracene-Assisted Morphology Optimization in Photoactive Layer for High-Efficiency Polymer Solar Cells

Currently, morphology optimization methods for the fused-ring nonfullerene acceptor-based polymer solar cells (PSCs) empirically follow the treatments originally developed in fullerene-based systems, being unable to meet the diverse molecular structures and strong crystallinity of the nonfullerene acceptors. Herein, a new and universal morphology controlling method is developed by applying volatilizable anthracene as solid additive. The strong crystallinity of anthracene offers the possibility to restrict the over aggregation of fused-ring nonfullerene acceptor in the process of film formation. During the kinetic process of anthracene removal in the blend under thermal annealing, donor can imbed into the remaining space of anthracene in the acceptor matrix to form well-developed nanoscale phase separation with bi-continuous interpenetrating networks. Consequently, the treatment of anthracene additive enables the power conversion efficiency (PCE) of PM6:Y6-based devices to 17.02%, which is a significant improvement with regard to the PCE of 15.60% for the reference device using conventional treatments. Moreover, this morphology controlling method exhibits general application in various active layer systems to achieve better photovoltaic performance. Particularly, a remarkable PCE of 17.51% is achieved in the ternary PTQ10:Y6:PC₇₁BM-based PSCs processed by anthracene additive. The morphology optimization strategy established in this work can offer unprecedented opportunities to build state-of-the-art PSCs.     

High-Efficiency (16.93%) Pseudo-Planar Heterojunction Organic Solar Cells Enabled by Binary Additives Strategy

Acquiring precision adjustable morphology of the blend films to improve the efficiency of charge separation and collection is a constant goal of organic solar cells (OSCs). Here, the above problem is improved by synergistically combining the sequential deposition (SD) method and the additive general strategy. By adding one additive 1,10-decanediol (DDO) into PM6 and another 1-chloronaphthalene (CN) into Y6, the molecule orientation of PM6 and the crystallite texture of the Y6 all become order. During the SD processing, a vertical phase separation OSCs device is formed where the donor enrichment at the anode and acceptor enrichment at the cathode. In comparison, the SD OSCs device with only CN additive still displays the bulk-heterojunction morphology similar to PM6:Y6 blend film. The morphology with vertical phase distribution can not only inhibit charge recombination but also facilitate charge collection, finally enhancing the fill factor (FF) and photocurrent in binary additives SD-type OSCs. As a result, the binary additives SD-type OSCs with blend film PM6 + DDO/Y6 + CN exhibit a high FF of 77.45%, enabling a power conversion efficiency as high as 16.93%. This work reveals a simple but effective approach for boosting high-efficiency OSCs with ideal morphologies and demonstrates that the additive is a promising processing alternative.