Designing 1,5‐Naphthyridine‐2,6‐dione‐Based Conjugated Polymers for Higher Crystallinity and Enhanced Light Absorption to Achieve 9.63% Efficiency Polymer Solar Cells

Highly crystalline conjugated polymers represent a key material for producing high‐performance thick‐active‐layer polymer solar cells (PSCs). However, despite their potential, a limited number of crystalline polymers are used in PSCs because of the lack of highly coplanar acceptor building blocks and insufficient light absorptivity (α < 10⁵) of most donor (D)–acceptor (A)‐type polymers. This study reports a series of novel 3,7‐di(thiophen‐2‐yl)‐1,5‐naphthyridine‐2,6‐dione (NTDT) acceptor‐based conjugated polymers, PNTDT‐2T, PNTDT‐TT, and PNTDT‐2F2T, synthesized with 2,2′‐bithiophene (2T), thieno[3,2‐b]thiophene (TT), and 3,3′‐difluoro‐2,2′‐bithiophene (2F2T) donor units, respectively. PNTDT‐2F2T exhibits superior polymer crystallinity and a much higher absorption coefficient than those of PNTDT‐2T or PNTDT‐TT because of adequate matching between highly coplanar A (NTDT) and D (2F2T) building blocks. A bulk heterojunction solar cell based on PNTDT‐2F2T exhibits a power conversion efficiency of up to 9.63%, with a high short circuit current of 18.80 mA cm^?2 and fill factor of 0.70, when a thick active layer (>200 nm) is used, without postfabrication hot processing. The findings demonstrate that the polymer crystallinity and absorption coefficient can be effectively controlled by selecting appropriate D and A building blocks, and that NTDT is a novel and versatile A building block for highly efficient thick‐active‐layer PSCs.     

Understanding the Impact of Oligomeric Polystyrene Side Chain Arrangement on the All‐Polymer Solar Cell Performance

The introduction of oligomeric polystyrene (PS) side chains into the conjugated backbone is proven to enhance the processability and electronic properties of semiconducting polymers. Here, two series of donor and acceptor polymers are prepared with different molar percentages of PS side chains to elucidate the effect of their substitution arrangement on the all‐polymer solar cell performance. The observed device performance is lower when the PS side chains are substituted on the donor polymer and higher when on the acceptor polymer, indicating a clear arrangement effect of the PS side chain. The incorporation of PS side chains to the acceptor polymer contributes to the decrease in phase separation domain size in the blend films. However, the reduced domain size was still an order of magnitude larger than the typical exciton diffusion length. A detailed morphological study together with the estimation of solubility parameter of the pristine PS, donor, and acceptor polymers reveals that the relative value of solubility parameter of each component dominantly contributes to the purity of the phase separated domain, which strongly impacts the amount of generated photocurrent and overall solar cell performance. This study provides an understanding of the design strategies to improve the all‐polymer solar cells.     

Impact of Noncovalent Sulfur–Fluorine Interaction Position on Properties,Structures, and Photovoltaic Performance in Naphthobisthiadiazole‐Based Semiconducting Polymers

Controlling the energetics and backbone order of semiconducting polymers is essential for the performance improvement of polymer‐based solar cells. The use of fluorine as the substituent for the backbone is known to effectively deepen the molecular orbital energy levels and coplanarize the backbone by noncovalent interactions with sulfur of the thiophene ring. In this work, novel semiconducting polymers are designed and synthesized based on difluoronaphthobisthiadiazole (FNTz) as a new family of naphthobisthiadiazole (NTz)–quaterthiophene copolymer systems, which are one of the highest performing polymers in solar cells. The effect of the fluorination position on the energetics and backbone order is systematically studied. It is found that the dependence of the solar cell fill factor on the active layer thickness is very sensitive to the fluorination position. It is thus further investigated and discussed how the structural features of the polymers influence the photovoltaic parameters as well as the diode characteristics and bimolecular recombination. Further, the polymer with fluorine on both the naphthobisthiadiazole and quaterthiophene moieties exhibits a quite high power conversion efficiency of 10.8% in solar cells in combination with a fullerene. It is believed that the results would offer new insights into the development of semiconducting polymers.     

Slot‐Die Coating of a High Performance Copolymer in a Readily Scalable Roll Process for Polymer Solar Cells

Copolymers based on dithieno[3,2‐b:2′,3′‐d]silole (DTS) and dithienylthiazolo[5,4‐d]thiazole (TTz) are synthesized and tested in an all‐solution roll process for polymer solar cells (PSCs). Fabrication of polymer:[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) solar cells is done on a previously reported compact coating/printing machine, which enables the preparation of PSCs that are directly scalable with full roll‐to‐roll processing. The positioning of the side‐chains on the thiophene units proves to be very significant in terms of solubility of the polymers and consequently has a major impact on the device yield and process control. The most successful processing is accomplished with the polymer, PDTSTTz‐4 , that has the side‐chains situated in the 4‐position on the thiophene units. Inverted PSCs based on PDTSTTz‐4 demonstrate high fill factors, up to 59%, even with active layer thicknesses well above 200 nm. Power conversion efficiencies of up to 3.5% can be reached with the roll‐coated PDTSTTz‐4 :PCBM solar cells that, together with good process control and high device yield, designate PDTSTTz‐4 as a convincing candidate for high‐throughput roll‐to‐roll production of PSCs.     

Effect of Molecular Orientation of Donor Polymers on Charge Generation and Photovoltaic Properties in Bulk Heterojunction All‐Polymer Solar Cells

All‐polymer solar cells (all‐PSCs) utilizing p‐type polymers as electron‐donors and n ‐typepolymers as electron‐acceptors have attracted a great deal of attention, and their efficiencies have been improved considerably. Here, five polymer donors with different molecular orientations are synthesized by random copolymerization of 5‐fluoro‐2,1,3‐benzothiadiazole with different relative amounts of 2,2′‐bithiophene (2T) and dithieno[3,2‐b;2′,3′‐d]thiophene (DTT). Solar cells are prepared by blending the polymer donors with a naphthalene diimide‐based polymer acceptor (PNDI) or a [6,6]‐phenyl C₇₁‐butyric acid methyl ester (PC₇₁BM) acceptor and their morphologies and crystallinity as well as optoelectronic, charge‐transport and photovoltaic properties are studied. Interestingly, charge generation in the solar cells is found to show higher dependence on the crystal orientation of the donor polymer for the PNDI‐based all‐PSCs than for the conventional PC₇₁BM‐based PSCs. As the population of face‐on‐oriented crystallites of the donor increased in PNDI‐based PSC, the short‐circuit current density (J_SC) and external quantum efficiency of the devices are found to significantly improve. Consequently, device efficiency was enhanced of all‐PSC from 3.11% to 6.01%. The study reveals that producing the same crystal orientation between the polymer donor and acceptor (face‐on/face‐on) is important in all‐PSCs because they provide efficient charge transfer at the donor/acceptor interface.     

Effect of Alkylsilyl Side‐Chain Structure on Photovoltaic Properties of Conjugated Polymer Donors

Side‐chain engineering is an important strategy for optimizing photovoltaic properties of organic photovoltaic materials. In this work, the effect of alkylsilyl side‐chain structure on the photovoltaic properties of medium bandgap conjugated polymer donors is studied by synthesizing four new polymers J70 , J72 , J73 , and J74 on the basis of highly efficient polymer donor J71 by changing alkyl substituents of the alkylsilyl side chains of the polymers. And the photovoltaic properties of the five polymers are studied by fabricating polymer solar cells (PSCs) with the polymers as donor and an n‐type organic semiconductor (n‐OS) m‐ITIC as acceptor. It is found that the shorter and linear alkylsilyl side chain could afford ordered molecular packing, stronger absorption coefficient, higher charge carrier mobility, thus results in higher J_sc and fill factor values in the corresponding PSCs. While the polymers with longer or branched alkyl substituents in the trialkylsilyl group show lower‐lying highest occupied molecular orbital energy levels which leads to higher V_oc of the PSCs. The PSCs based on J70 :m‐ITIC and J71 :m‐ITIC achieve power conversion efficiency (PCE) of 11.62 and 12.05%, respectively, which are among the top values of the PSCs reported in the literatures so far.     

Extended Conjugation Length of Nonfullerene Acceptors with Improved Planarity via Noncovalent Interactions for High‐Performance Organic Solar Cells

Three low‐bandgap nonfullerene acceptors (NFAs) IDTO‐T‐4F, IDTO‐Se‐4F, and IDTO‐TT‐4F with extended conjugation length are designed and synthesized. Various π‐spacers, thiophene, selenophene, and thieno[3,2‐b]thiophene are incorporated to extend the conjugated length and enhance the backbone planarity via noncovalent O···S or O···Se interactions. These NFAs exhibit strong light absorption in the range of 600–900 nm with narrow bandgaps between 1.38 and 1.45 eV. By blending with a wide‐bandgap donor material PBDB‐T, organic solar cells (OSCs) based on these NFAs all yield high efficiency over 10% with low energy losses ranging from 0.52 to 0.59 eV. Importantly, as a result of relatively high lowest unoccupied molecular orbital level, large hole and electron mobility in blend film, and low charge carrier recombination loss, optimized devices based on IDTO‐T‐4F exhibit a large open‐circuit voltage of 0.864 V, a high short‐circuit current density of 20.12 mA cm^?2, and a notable fill factor of 72.7%, leading to an impressive efficiency of 12.62%, which represents the best performance for NFA OSCs using noncovalent interactions in acceptor molecule design. The results indicate that optimizing the conjugation length and backbone planarity via intramolecular noncovalent O···S or O···Se interactions is a useful strategy for NFA materials invention toward high‐performance solar cells.     

Medium Bandgap Polymer Donor Based on Bi(trialkylsilylthienyl‐benzo[1,2‐b:4,5‐b′]‐difuran) for High Performance Nonfullerene Polymer Solar Cells

A new 2D‐conjugated medium bandgap donor–acceptor copolymer, J81 , based on benzodifuran with trialkylsilyl thiophene side chains as donor unit and fluorobenzothiazole as acceptor, is synthesized and successfully used in nonfullerene polymer solar cells (PSCs) with low bandgap n‐type organic semiconductor (n‐OS) 3,9‐bis(2‐methylene‐ (3‐(1,1‐dicyanomethylene)‐indanone)‐5,5,11,11‐tetrakis(4‐ hexylphenyl)‐dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]‐ dithiophene (ITIC) and m ‐ITIC as acceptor. J81 possesses a lower‐lying highest occupied molecular orbital (HOMO) energy level of ?5.43 eV and medium bandgap of 1.93 eV with complementary absorption in the visible–near infrared region with the n‐OS acceptor. The PSCs based on J81 :ITIC and J81 :m ‐ITIC yield high power conversion efficiency of 10.60% and 11.05%, respectively, with high V _oc of 0.95–0.96 V benefit from the lower‐lying HOMO energy level of J81 donor. The work indicates that J81 is another promising polymer donor for the nonfullerene PSCs.     

Roll‐to‐Roll Printed Large‐Area All‐Polymer Solar Cells with 5% Efficiency Based on a Low Crystallinity Conjugated Polymer Blend

The challenge of continuous printing in high‐efficiency large‐area organic solar cells is a key limiting factor for their widespread adoption. A materials design concept for achieving large‐area, solution‐coated all‐polymer bulk heterojunction solar cells with stable phase separation morphology between the donor and acceptor is presented. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity, and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, the results show that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers. This methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small‐scale solution shearing coater to a large‐scale continuous roll‐to‐roll (R2R) printer. Large‐area all‐polymer solar cells are continuously roll‐to‐roll slot die printed with power conversion efficiencies of 5%, with combined cell area up to 10 cm². This is among the highest efficiencies realized with R2R‐coated active layer organic materials on flexible substrate.     

Critical Role of Polymer Aggregation and Miscibility in Nonfullerene‐Based Organic Photovoltaics

Understanding the correlation between polymer aggregation, miscibility, and device performance is important to establish a set of chemistry design rules for donor polymers with nonfullerene acceptors (NFAs). Employing a donor polymer with strong temperature‐dependent aggregation, namely PffBT4T‐2OD [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)], also known as PCE‐11 as a base polymer, five copolymer derivatives having a different thiophene linker composition are blended with the common NFA O‐IDTBR to investigate their photovoltaic performance. While the donor polymers have similar optoelectronic properties, it is found that the device power conversion efficiency changes drastically from 1.8% to 8.7% as a function of thiophene content in the donor polymer. Results of structural characterization show that polymer aggregation and miscibility with O‐IDTBR are a strong function of the chemical composition, leading to different donor–acceptor blend morphology. Polymers having a strong tendency to aggregate are found to undergo fast aggregation prior to liquid–liquid phase separation and have a higher miscibility with NFA. These properties result in smaller mixed donor–acceptor domains, stronger PL quenching, and more efficient exciton dissociation in the resulting cells. This work indicates the importance of both polymer aggregation and donor–acceptor interaction on the formation of bulk heterojunctions in polymer:NFA blends.     

Dopant‐Free,Donor–Acceptor‐Type Polymeric Hole‐Transporting Materials for the Perovskite Solar Cells with Power Conversion Efficiencies over 20%

The rich molecular design of electron donor (D)–acceptor (A) polymers offers many valuable clues to obtain high‐efficiency hole‐transporting materials (HTMs) for use in perovskite solar cells (PVSCs). The fused aromatic or heteroaromatic units can increase the conjugation of the polymer backbone to facilitate electron delocalization, which increases the rigidity of adjacent units to prevent rotational disorder and lower the reorganization energy, leading to improved carrier mobility and optimized film morphology. In this work, fused‐ring ladder‐type indacenodithiophene and indacenodithieno[3,2‐b]thiophene are used as D units, benzodithiophene‐4,8‐dione as the A unit, and thienothiophene as a π‐bridge to form the D–A polymers PBDTT and PBTTT, respectively. Both polymers exhibit favorable properties as HTMs including suitable energy levels, high hole mobility, and excellent film quality. Both dopant‐free HTMs endow n‐i‐p PVSCs with promising performance and stability. A maximum power conversion efficiency of 20.28% is achieved for PBDTT‐based devices, which is among the highest values reported to date.     

Thick Film Polymer Solar Cells Based on Naphtho[1,2‐c:5,6‐c]bis[1,2,5]thiadiazole Conjugated Polymers with Efficiency over 11%

Two novel narrow bandgap π‐conjugated polymers based on naphtho[1,2‐c:5,6‐c′]bis([1,2,5]thiadiazole) (NT) unit are developed, which contain the thiophene or benzodithiophene flanked with alkylthiophene as the electron‐donating segment. Both copolymers exhibit strong aggregations both in solution and as thin films. The resulting copolymers with higher molecular weight show higher photovoltaic performance by virtue of the enhanced short‐circuit current densities and fill factors, which can be attributed to their higher absorptivity and formation of more favorable film morphologies. Polymer solar cells (PSCs) fabricated with the copolymer PNTT achieve remarkable power conversion efficiencies (PCEs) > 11% based on both conventional and inverted structures at the photoactive layer thickness of 280 nm, which is the highest value so far observed from NT‐based copolymers. Of particular interest is that the device performances are insensitive to the thickness of the photoactive layer, for which the PCEs > 10% can be achieved with film thickness ranging from 150 to 660 nm, and the PCE remains >9% at the thickness over 1 µm. These findings demonstrate that these NT‐based copolymers can be promising candidates for the construction of thick film PSCs toward low‐cost roll‐to‐roll processing technology.     

A Thieno[3,2‐c]Isoquinolin‐5(4H)‐One Building Block for Efficient Thick‐Film Solar Cells

An aromatic lactam acceptor unit, thieno[3,2‐c]isoquinolin‐5(4H)‐one (TIQ), is developed. Compared with its analogues, dithieno[3,2‐b:2′,3′‐d]pyridin‐5(4H)‐one (DTP) and phenanthridin‐6(5H)‐one (PN), TIQ shows its advantage in constructing donor–acceptor (D–A) copolymers for efficient solar cells. TIQ‐based D–A copolymer PTIQ4TFBT delivers a power conversion efficiency (PCE) of 10.16% in polymer:fullerene solar cells, while those based on DTP and PN copolymers, PDTP4TFBT and PPN4TFBT, afford PCEs around 8.5%. The higher performance of PTIQ4TFBT:PC₇₁BM solar cells originates from enhanced short‐circuit current density (J_sc) and fill factor (FF), because of favorable morphology, less bimolecular recombination, and balanced charge transport in the active layer. Moreover, the performance for PTIQ4TFBT:PC₇₁BM solar cells is less sensitive to active layer thickness than PDTP4TFBT:PC₇₁BM and PPN4TFBT:PC₇₁BM solar cells. Over 8% PCEs can be obtained from PTIQ4TFBT:PC₇₁BM solar cells when the active layer thickness is over 500 nm.     

π‐Extended Narrow‐Bandgap Diketopyrrolopyrrole‐Based Oligomers for Solution‐Processed Inverted Organic Solar Cells

A series of narrow‐bandgap π‐conjugated oligomers based on diketopyrrolopyrrole chromophoric units coupled with benzodithiophene, indacenodithiophene, thiophene, and isoindigo cores are designed and synthesized for application as donor materials in solution‐processed small‐molecule organic solar cells. The impacts of these different central cores on the optoelectronic and morphological properties, carrier mobility, and photovoltaic performance are investigated. These π‐extended oligomers possess broad and intense optical absorption covering the range from 550 to 750 nm, narrow optical bandgaps of 1.52–1.69 eV, and relatively low‐lying highest occupied molecular orbital (HOMO) energy levels ranging from ?5.24 to ?5.46 eV in their thin films. A high power conversion efficiency of 5.9% under simulated AM 1.5G illumination is achieved for inverted organic solar cells based on a small‐molecule bulk‐heterojunction system consisting of a benzodithiophene‐diketopyrrolopyrrole‐containing oligomer as a donor and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as an acceptor. Transmission electron microscopy and energy‐dispersive X‐ray spectroscopy reveal that interpenetrating and interconnected donor/acceptor domains with pronounced mesoscopic phase segregation are formed within the photoactive binary blends, which is ideal for efficient exciton dissociation and charge transport in the bulk‐heterojunction devices.     

Loss Mechanisms in Thick‐Film Low‐Bandgap Polymer Solar Cells

Polymer bulk heterojunction solar cells based on low bandgap polymer:fullerene blends are promising for next generation low‐cost photovoltaics. While these solution‐processed solar cells are compatible with large‐scale roll‐to‐roll processing, active layers used for typical laboratory‐scale devices are too thin to ensure high manufacturing yields. Furthermore, due to the limited light absorption and optical interference within the thin active layer, the external quantum efficiencies (EQEs) of bulk heterojunction polymer solar cells are severely limited. In order to produce polymer solar cells with high yields, efficient solar cells with a thick active layer must be demonstrated. In this work, the performance of thick‐film solar cells employing the low‐bandgap polymer poly(dithienogermole‐thienopyrrolodione) (PDTG‐TPD) was demonstrated. Power conversion efficiencies over 8.0% were obtained for devices with an active layer thickness of 200 nm, illustrating the potential of this polymer for large‐scale manufacturing. Although an average EQE > 65% was obtained for devices with active layer thicknesses > 200 nm, the cell performance could not be maintained due to a reduction in fill factor. By comparing our results for PDTG‐TPD solar cells with similar P3HT‐based devices, we investigated the loss mechanisms associated with the limited device performance observed for thick‐film low‐bandgap polymer solar cells.     

The Importance of Fullerene Percolation in the Mixed Regions of Polymer–Fullerene Bulk Heterojunction Solar Cells

Most optimized donor‐acceptor (D‐A) polymer bulk heterojunction (BHJ) solar cells have active layers too thin to absorb greater than ～80% of incident photons with energies above the polymer's band gap. If the thickness of these devices could be increased without sacrificing internal quantum efficiency, the device power conversion efficiency (PCE) could be significantly enhanced. We examine the device characteristics of BHJ solar cells based on poly(di(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene‐co‐octylthieno[3,4‐c]pyrrole‐4,6‐dione) (PBDTTPD) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) with 7.3% PCE and find that bimolecular recombination limits the active layer thickness of these devices. Thermal annealing does not mitigate these bimolecular recombination losses and drastically decreases the PCE of PBDTTPD BHJ solar cells. We characterize the morphology of these BHJs before and after thermal annealing and determine that thermal annealing drastically reduces the concentration of PCBM in the mixed regions, which consist of PCBM dispersed in the amorphous portions of PBDTTPD. Decreasing the concentration of PCBM may reduce the number of percolating electron transport pathways within these mixed regions and create morphological electron traps that enhance charge‐carrier recombination and limit device quantum efficiency. These findings suggest that (i) the concentration of PCBM in the mixed regions of polymer BHJs must be above the PCBM percolation threshold in order to attain high solar cell internal quantum efficiency, and (ii) novel processing techniques, which improve polymer hole mobility while maintaining PCBM percolation within the mixed regions, should be developed in order to limit bimolecular recombination losses in optically thick devices and maximize the PCE of polymer BHJ solar cells.     

Efficient Non‐Fullerene Organic Photovoltaic Modules Incorporating As‐Cast and Thickness‐Insensitive Photoactive Layers

In this work, a new combination of a wide bandgap polymer poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]‐dithiophene‐alt‐N‐(2‐hexyldecyl)‐5′5‐bis[3‐(decylthio)thiophene‐2‐yl]‐2′2‐bithiophene‐3′3‐dicarboximide] (PBTIBDTT) and a non‐fullerene small molecule acceptor based on a bulky seven‐ring fused core (indacenodithieno[3,2‐b]thiophene) end‐capped with 2‐(3‐oxo‐2,3‐dihydroinden‐1‐ylidene)malononitrile groups with one fluorine substituent (ITIC‐F) is proposed, and as‐cast non‐fullerene organic solar cells (NFOSCs) with 11.2% efficiency are achieved. The device efficiencies are also insensitive to the variation of photoactive layer (PAL) thickness and can maintain over 9% efficiency as PAL thickness increases to 350 nm, which is one of the best results for as‐cast organic solar cells. More importantly, non‐fullerene organic photovoltaic (OPV) modules are demonstrated via laser ablation technique for the first time, which delivers a record efficiency of 8.6% (with active area of 3.48 cm²) among large‐area OPV modules. Furthermore, the morphology and performance evolutions of the as‐cast NFOSCs and the ones processed with solvent additive are systematically investigated. The results demonstrate the great advantage of as‐cast solar cells in achieving constant morphology and high performance with thick PALs. The NFOSCs fabricated with simple procedure, insensitive to film thickness and compatible with large‐area OPV modules, show significant potential for application the future.     

Tuning Energy Levels without Negatively Affecting Morphology: A Promising Approach to Achieving Optimal Energetic Match and Efficient Nonfullerene Polymer Solar Cells

One advantage of nonfullerene polymer solar cells (PSCs) is that they can yield high open‐circuit voltage (V_OC) despite their relatively low optical bandgaps. To maximize the V_OC of PSCs, it is important to fine‐tune the energy level offset between the donor and acceptor materials, but in a way not negatively affecting the morphology of the donor:acceptor (D:A) blends. Here, an effective material design rationale based on a family of D–A1–D–A2 terthiophene (T3) donor polymers is reported, which allows for the effective tuning of energy levels but without any negative impacts on the morphology of the blend. Based on a T3 donor unit combined with difluorobenzothiadiazole (ffBT) and difluorobenzoxadiazole (ffBX) acceptor units, three donor polymers are developed with highly similar morphological properties. This is particularly surprising considering that the corresponding quaterthiophene polymers based on ffBT and ffBX exhibit dramatic differences in their solubility and morphological properties. With the fine‐tuning of energy levels, the T3 polymers yield nonfullerene PSCs with a high efficiency of 9.0% for one case and with a remarkably low energy loss (0.53 V) for another polymer. This work will facilitate the development of efficient nonfullerene PSCs with optimal energy levels and favorable morphology properties.     

Comparing the Device Physics and Morphology of Polymer Solar Cells Employing Fullerenes and Non‐Fullerene Acceptors

There is a need to find electron acceptors for organic photovoltaics that are not based on fullerene derivatives since fullerenes have a small band gap that limits the open‐circuit voltage (V_OC), do not absorb strongly and are expensive. Here, a phenylimide‐based acceptor molecule, 4,7‐bis(4‐(N‐hexyl‐phthalimide)vinyl)benzo[c]1,2,5‐thiadiazole (HPI‐BT), that can be used to make solar cells with V_OC values up to 1.11 V and power conversion efficiencies up to 3.7% with two thiophene polymers is demonstrated. An internal quantum efficiency of 56%, compared to 75–90% for polymer‐fullerene devices, results from less efficient separation of geminate charge pairs. While favorable energetic offsets in the polymer‐fullerene devices due to the formation of a disordered mixed phase are thought to improve charge separation, the low miscibility (<5 wt%) of HPI‐BT in polymers is hypothesized to prevent the mixed phase and energetic offsets from forming, thus reducing the driving force for charges to separate into the pure donor and acceptor phases where they can be collected.     

Photoactive Blend Morphology Engineering through Systematically Tuning Aggregation in All‐Polymer Solar Cells

Polymer aggregation plays a critical role in the miscibility of materials and the performance of all‐polymer solar cells (APSCs). However, many aspects of how polymer texturing and aggregation affect photoactive blend film microstructure and photovoltaic performance are poorly understood. Here the effects of aggregation in donor–acceptor blends are studied, in which the number‐average molecular weights (M_ns) of both an amorphous donor polymer, poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b;4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐)‐2‐carboxylate‐2‐6‐diyl)] ( PBDTT‐FTTE ) and a semicrystalline acceptor polymer, poly{[N,N′‐bis(2‐octyldodecyl)naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} ( P(NDI2OD‐T2) ) are systematically varied. The photovoltaic performance is correlated with active layer microstructural and optoelectronic data acquired by in‐depth transmission electron microscopy, grazing incidence wide‐angle X‐ray scattering, thermal analysis, and optical spectroscopic measurements. Coarse‐grained modeling provides insight into the effects of polymer aggregation on the blend morphology. Notably, the computed average distance between the donor and the acceptor polymers correlates well with solar cell photovoltaic metrics such as short‐circuit current density (J_sc) and represents a useful index for understanding/predicting active layer blend material intermixing trends. Importantly, these results demonstrate that for polymers with different texturing tendencies (amorphous/semicrystalline), the key for optimal APSC performance, photovoltaic blend morphology can be controlled via both donor and acceptor polymer aggregation.