Side‐Chain Engineering for Fine‐Tuning of Energy Levels and Nanoscale Morphology in Polymer Solar Cells

A series of four polymers containing benzo[1,2‐b:4,5‐b′]dithiophene (BDT) and 5,6‐difluoro‐4,7‐diiodobenzo[c][1,2,5]thiadiazole (2FBT), PBDT2FBT, PBDT2FBT‐O, PBDT2FBT‐T, and PBDT2FBT‐T‐O, are synthesized with their four different side chains, alkyl‐, alkoxy‐, alkylthienyl‐, and alkoxythienyl. Experimental results and theoretical calculations show that the molecular tuning of the side chains simultaneously influences the solubilities, energy levels, light absorption, surface tension, and intermolecular packing of the resulting polymers by altering their molecular coplanarity and electron affinity. The polymer solar cell (PSC) based on a blend of PBDT2FBT‐T/[6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) exhibits the best photovoltaic performance of the four PBDT2FBT derivatives, with a high open‐circuit voltage of 0.98 V and a power conversion efficiency of 6.37%, without any processing additives, post‐treatments, or optical spacers. Furthermore, PBDT2FBT‐T‐O, which has a novel side chain alkoxythienyl, showed promising properties with the most red‐shifted absorption and strong intermolecular packing property in solid state. This study provides insight into molecular design and fabrication strategies via structural tuning of the side chains of conjugated polymers for achieving highly efficient PSCs.     

Significantly Enhancing the Efficiency of a New Light‐Harvesting Polymer with Alkylthio naphthyl Substituents Compared to Their Alkoxyl Analogs

In this work, a new benzo[1,2‐b:4,5‐b′]dithiophene (BDT) building block containing alkylthio naphthyl as a side chain is designed and synthesized, and the resulting polymer, namely PBDTNS‐BDD, shows a lower HOMO energy level than that of its alkoxyl naphthyl counterpart PBDTNO‐BDD. An optimized photovoltaic device using PBDTNS‐BDD as a donor exhibits power conversion efficiencies (PCE) of 8.70% and 9.28% with the fullerene derivative PC₇₁BM and the fullerene‐free small molecule ITIC as acceptors, respectively. Surprisingly, ternary blend devices based on PBDTNS‐BDD and two acceptors, namely PC₇₁BM and ITIC, shows a PCE of 11.21%, which is much higher than that of PBDTNO‐BDD based ternary devices (7.85%) even under optimized conditions.     

Investigation of Charge Carrier Behavior in High Performance Ternary Blend Polymer Solar Cells

This study demonstrates high‐performance, ternary‐blend polymer solar cells by modifying a binary blend bulk heterojunction (PPDT2FBT:PC₇₁BM) with the addition of a ternary component, PPDT2CNBT. PPDT2CNBT is designed to have complementary absorption and deeper frontier energy levels compared to PPDT2FBT, while being based on the same polymeric backbone. A power conversion efficiency of 9.46% is achieved via improvements in both short‐circuit current density (J_SC) and open‐circuit voltage (V_OC). Interestingly, the V_OC increases with increasing the PPDT2CNBT content in ternary blends. In‐depth studies using ultraviolet photoelectron spectroscopy and transient absorption spectroscopy indicate that the two polymers are not electronically homogeneous and function as discrete light harvesting species. The structural similarity between PPDT2CNBT and PPDT2FBT allows the merits of a ternary system to be fully utilized to enhance both J_SC and V_OC without detriment to fill‐factor via minimized disruption of semi‐crystalline morphology of binary PPDT2FBT:PC₇₁BM blend. Further, by careful analysis, charge carrier transport in this ternary blend is clearly verified to follow parallel‐like behavior.     

A High‐Performance D–A Copolymer Based on Dithieno[3,2‐b:2′,3′‐d]Pyridin‐5(4H)‐One Unit Compatible with Fullerene and Nonfullerene Acceptors in Solar Cells

Development of high‐performance donor–acceptor (D–A) copolymers is vital in the research of polymer solar cells (PSCs). In this work, a low‐bandgap D–A copolymer based on dithieno[3,2‐b:2′,3′‐d]pyridin‐5(4H)‐one unit (DTP), PDTP4TFBT, is developed and used as the donor material for PSCs with PC₇₁BM or ITIC as the acceptor. PDTP4TFBT:PC₇₁BM and PDTP4TFBT:ITIC solar cells give power conversion efficiencies (PCEs) up to 8.75% and 7.58%, respectively. 1,8‐Diiodooctane affects film morphology and device performance for fullerene and nonfullerene solar cells. It inhibits the active materials from forming large domains and improves PCE for PDTP4TFBT:PC₇₁BM cells, while it promotes the aggregation and deteriorates performance for PDTP4TFBT:ITIC cells. The ternary‐blend cells based on PDTP4TFBT:PC₇₁BM:ITIC (1:1.2:0.3) give a decent PCE of 9.20%.     

Influence of Fullerene Acceptor on the Performance,Microstructure, and Photophysics of Low Bandgap Polymer Solar Cells

The morphology, photophysics, and device performance of solar cells based on the low bandgap polymer poly[[2,6′‐4,8‐di(5‐ethylhexylthienyl)benzo[1,2‐b;3,3‐b]dithiophene]3‐fluoro‐2[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl (PBDTTT‐EFT) (also known as PTB7‐Th) blended with different fullerene acceptors: Phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM), phenyl‐C₇₁ ‐butyric acid methyl ester (PC₇₁BM), or indene‐C₆₀ bisadduct (ICBA) are correlated. Compared to PC₇₁ BM‐based cells – which achieve a power conversion efficiency (PCE) of 9.4% – cells using ICBA achieve a higher open‐circuit voltage (V_OC) of 1.0 V albeit with a lower PCE of 7.1%. To understand the origin of this lower PCE, the morphology and photophysics have been thoroughly characterized. Hard and soft X‐ray scattering measurements reveal that the PBDTTT‐EFT:ICBA blend has a lower crystallinity, lower domain purity, and smaller domain size compared to the PBDTTT‐EFT:PC₇₁BM blend. Incomplete photoluminescence quenching is also found in the ICBA blend with transient absorption measurements showing faster recombination dynamics at short timescales. Transient photovoltage measurements highlight further differences in recombination at longer timeframes due to the more intermixed morphology of the ICBA blend. Interestingly, a mild thermal treatment improves the performance of PBDTTT‐EFT:ICBA cells which is exploited in the fabrication of a homo PBDTTT‐EFT:ICBA tandem solar cell with PCE of 9.0% and V_OC of 1.93 V.     

Impact of Fullerene Molecular Weight on P3HT:PCBM Microstructure Studied Using Organic Thin‐Film Transistors

The clustering and diffusion of C₇₁‐butyric acid methyl ester (PC₇₁BM) in poly(3‐hexylthiophene) (P3HT) has been studied using single layer blend and bilayer organic field‐effect transistors (OFETs) and by atomic force microscopy (AFM). P3HT:PC₇₁BM blend based OFETs were found to undergo phase‐segregation upon annealing, which was detectable as a fall in electron mobility with increasing annealing temperature. By employing carefully designed bilayer P3HT:PC₇₁BM OFETs, the diffusion‐properties of PC₇₁BM in P3HT could additionally be inferred from electron mobility measurements. It was found that the prerequisite annealing temperatures for detectable PC₇₁BM clustering and diffusion in P3HT was approximately 20 °C higher than for PC₆₁BM. The diffusion coefficient of PC₆₁BM in P3HT was found to be several times higher that that of PC₇₁BM. The present work provides unique insights into the diffusion process of fullerenes in conjugated polymers and could prove highly valuable for future materials development and device optimization.     

Feasible D1–A–D2–A Random Copolymers for Simultaneous High‐Performance Fullerene and Nonfullerene Solar Cells

A series of PBDB‐TTn random donor copolymers is synthesized, consisting of an electron‐deficient benzo[1,2‐c:4,5‐c′]dithiophene‐4,8‐dione (BDD) unit and different ratios of two electron‐rich benzo[1,2‐b:4,5‐b′]dithiophene (BDT) and thieno[3,2‐b]thiophene (TT) units, with intention to modulate the intrachain and/or interchain interactions and ultimately bulk‐heterojunction morphology evolution. A comparative study using 4 × 2 polymer solar cell (PSC) performance maps and each of the [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) and the fused‐aromatic‐ring‐based molecule (m‐ITIC) acceptors are carried out. Given the similarities in their absorption ranges and energy levels, the PBDB‐TTn copolymers clearly reveal a change in the absorption coefficients upon optimization of the BDT to TT ratio in the backbone. Among the given acceptor combination sets, superior performances are observed in the case of PBDB‐TT5 blended with PC₇₁BM (8.34 ± 0.10%) or m‐ITIC (11.10 ± 0.08%), and the dominant factors causing power conversion efficiency differences in them are found to be distinctly different. For example, the performances of PC₇₁BM‐based PSCs are governed by size and population of face‐on crystallites, while intermixed morphology without the formation of large phase‐separated aggregates is the key factor for achieving high‐performance m‐ITIC‐based PSCs. This study presents a new sketch of structure–morphology–performance relationships for fullerene‐ versus nonfullerene‐based PSCs.     

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.     

Spectral Engineering of Semitransparent Polymer Solar Cells for Greenhouse Applications

In this study, a wavelength selective semitransparent polymer solar cell (ST‐PSC) with a proper transmission spectrum for plant growth is proposed for greenhouse applications. A ternary strategy combining a wide bandgap polymer donor with a near‐infrared absorbing nonfullerene acceptor and a high electron mobility fullerene acceptor is introduced to achieve PSCs with power conversion efficiency (PCE) over 10%. The addition of PC₇₁BM into J52:IEICO‐4F binary blend contributes to the suppressed trap‐assisted recombination, enhanced charge extraction, and improved open‐circuit voltage simultaneously. ST‐PSC based on the J52:IEICO‐4F:PC₇₁BM ternary blend shows an optimized performance with PCE of 7.75% and a defined crop growth factor of 24.8%. Such high‐performance ST‐PSC is achieved by carefully engineering the absorption spectrum of the light harvesting materials. As a result, the transmission spectra of the semitransparent devices are well‐matched with the absorption spectra of the photoreceptors, such as chlorophylls, in green plants, which provides adequate lighting conditions for photosynthesis and plant growth, and therefore making it a competitive candidate for photovoltaic greenhouse applications.     

The Effect of Fluorination in Manipulating the Nanomorphology in PTB7:PC71BM Bulk Heterojunction Systems

The best performing low bandgap copolymers PTB series to date which is based on thieno[3,4‐b]thiophene‐alt‐benzodithiophene units blended with [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC₇₁BM), have been the focus of polymer‐based solar cells. Here, novel fluorinated polymers PTB7‐Fx (fluorine units coupled with submonomer thieno[3,4‐b]thiophene) with varied degree of fluorination are used as electron donor materials. The PTB7‐Fx:PC₇₁BM bulk heterojunction (BHJ) films spin‐coated from the host solvent chlorobenzene without and with solvent additive 1,8‐diiodooctane (DIO) and the corresponding solar cell devices are systematically investigated to address the morphology‐efficiency relationship. Self‐assembled BHJ morphology is already observed for as‐spun blend films. After adding the solvent additive DIO, the pronounced ordered structures are suppressed and better intermixed films with much smaller domain sizes result. Full fluorination of the third C‐atom of thienothiophene gives rise to the highest power conversion efficiency. As the absorption properties, film morphology and crystallinity remain similar for different degrees of fluorination, the main influence of the photovoltaic performance is ascribed to the different lowest unoccupied molecular orbital (LUMO) of each polymer instead of the film morphology. Thus the device performance can be efficiently improved by tuning the energy level of the polymer without necessarily changing either the film nanomorphology or crystallinity dramatically.     

Highly Efficient Polymer Tandem Cells and Semitransparent Cells for Solar Energy

Highly efficient tandem and semitransparent (ST) polymer solar cells utilizing the same donor polymer blended with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as active layers are demonstrated. A high power conversion efficiency (PCE) of 8.5% and a record high open‐circuit voltage of 1.71 V are achieved for a tandem cell based on a medium bandgap polymer poly(indacenodithiophene‐co‐phananthrene‐quinoxaline) (PIDT‐phanQ). In addition, this approach can also be applied to a low bandgap polymer poly[2,6‐(4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7‐(5‐fluoro‐2,1,3‐benzothia‐diazole)] (PCPDTFBT), and PCEs up to 7.9% are achieved. Due to the very thin total active layer thickness, a highly efficient ST tandem cell based on PIDT‐phanQ exhibits a high PCE of 7.4%, which is the highest value reported to date for a ST solar cell. The ST device also possesses a desirable average visible transmittance (≈40%) and an excellent color rendering index (≈100), permitting its use in power‐generating window applications.     

Ultrafast Charge Generation Pathways in Photovoltaic Blends Based on Novel Star‐Shaped Conjugated Molecules

The quest for new materials is one of the main factors propelling recent advances in organic photovoltaics. Star‐shaped small molecules (SSMs) have been proven promising candidates as perspective donor material due to the increase in numbers of excitation pathways caused by the degeneracy of the lowest unoccupied molecular orbital (LUMO) level. In order to unravel the pathways of the initial photon‐to‐charge conversion, the photovoltaic blends based on three different SSMs with a generic structure of N(phenylene‐nthiophene‐dicyanovinyl‐alkyl)₃ (n = 1–3), and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) acceptor are investigated by ultrafast photoinduced absorption spectroscopy assisted by density functional theory calculations. It is shown that both electron transfer from SSMs to PC₇₁BM and hole transfer from PC₇₁BM to SSMs are equally significant for generation of long‐lived charges. In contrast, intramolecular (intra‐SSM) charge separation results in geminate recombination and therefore constitutes a loss channel. Overall, up to 60% of long‐lived separated charges are generated at the optimal PC₇₁BM concentrations. The obtained results suggest that further improvement of the SSM‐based solar cells is feasible via optimization of blend morphology and by suppressing the intra‐SSM recombination channel.     

Unraveling the Morphology of High Efficiency Polymer Solar Cells Based on the Donor Polymer PBDTTT‐EFT

The microstructure of the polymer PBDTTT‐EFT and blends with the fullerene derivative PC₇₁BM that achieve solar conversion efficiencies of over 9% is comprehensively investigated. A combination of synchrotron techniques are employed including surface‐sensitive near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy and bulk‐sensitive grazing‐incidence wide angle X‐ray scattering (GIWAXS). A preferential “face‐on” orientation of PBDTTT‐EFT is observed in the bulk of both pristine and blend thin films, with π–π stacking largely normal to the substrate, which is thought to be beneficial for charge transport. At the surface of the blend, a slight “edge‐on” structure of the polymer is observed with side‐chains aligned normal to the substrate. The effect of the solvent additive 1,8‐diiodooctane (DIO) on solar cell efficiency and film microstructure is also investigated, where the addition of 3 vol% DIO results in an efficiency increase from ≈6.4% to ≈9.5%. GIWAXS studies indicate that the addition of DIO improves the crystallization of the polymer. Furthermore, atomic force microscopy and transmission electron microscopy are employed to image surface and bulk morphology revealing that DIO suppresses the formation of large PC₇₁BM aggregates.     

Enhanced Photovoltaic Performance of Amorphous Donor–Acceptor Copolymers Based on Fluorine‐Substituted Benzodioxocyclohexene‐Annelated Thiophene

Donor–acceptor (D‐A) type π‐conjugated copolymers with crystalline behavior have been extensively investigated as donor semiconductors in organic photovoltaics (OPVs). On the other hand, the development of high‐performance amorphous donor materials is still behind. The amorphous donor copolymer DTS‐C₀(F₂) consisting of dithieno[3,2‐b:2′,3′‐d]silole ( DTS ) donor unit and the recently developed fluorine‐substituted naphtho[2,3‐c]thiophene‐4,9‐dione ( C₀(F₂) ) acceptor unit shows moderate photovoltaic performance upon blending with PC₇₁BM. In this work, to enhance the hole‐transporting characteristics, a 3‐hexylthiophene ( HT ) spacer unit is integrated into the conjugated backbone, resulting in a new amorphous copolymer DTS‐HT‐C₀(F₂) . The strong electron‐accepting nature of C₀(F₂) allows the introduction of the HT spacer without affecting the frontier orbital energies and thus the D‐A character. Without using solvent additives and thermal annealing, OPVs based on DTS‐HT‐C₀(F₂) and [6,6]‐phenyl‐C71‐butyric acid methyl ester PC₇₁BM show an improved power conversion efficiency of 9.12%. Investigation of the device physics unambiguously reveals that the hole mobility of the copolymer in the blend is increased by an order of magnitude by the introduction of HT , while keeping an amorphous film nature, leading to higher short‐circuit current density and fill factor. These results demonstrate the realization of high‐performance OPVs based on amorphous active layers.     

Layer‐by‐Layer Solution‐Processed Low‐Bandgap Polymer‐PC61BM Solar Cells with High Efficiency

Polymer solar cells (PSCs) are fabricated without solvent additives using a low‐bandgap polymer, PBDTTT‐C‐T, as the donor and [6,6]‐phenyl‐C61‐butyric‐acid‐methyl‐ester (PC₆₁BM) as the acceptor. Donor‐acceptor blend and layer‐by‐layer (LL) solution process are used to form active layers. Relative to the blend devices, the LL devices exhibit stronger absorption, better vertical phase separation, higher hole and electron mobilities, and better charge extraction at correct electrodes. As a result, after thermal annealing the LL devices exhibit an average power conversion efficiency (PCE) of 6.86%, which is much higher than that of the blend devices (4.31%). The best PCE of the LL devices is 7.13%, which is the highest reported for LL processed PSCs and among the highest reported for PC₆₁BM‐based single‐junction PSCs.     

Interplay Between Side Chain Pattern,Polymer Aggregation,and Charge Carrier Dynamics in PBDTTPD:PCBM Bulk‐Heterojunction Solar Cells

Poly(benzo[1,2‐b:4,5‐b′]dithiophene–alt–thieno[3,4‐c]pyrrole‐4,6‐dione) (PBDTTPD) polymer donors with linear side‐chains yield bulk‐heterojunction (BHJ) solar cell power conversion efficiencies (PCEs) of about 4% with phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as the acceptor, while a PBDTTPD polymer with a combination of branched and linear substituents yields a doubling of the PCE to 8%. Using transient optical spectroscopy it is shown that while the exciton dissociation and ultrafast charge generation steps are not strongly affected by the side chain modifications, the polymer with branched side chains exhibits a decreased rate of nongeminate recombination and a lower fraction of sub‐nanosecond geminate recombination. In turn the yield of long‐lived charge carriers increases, resulting in a 33% increase in short circuit current (J _sc). In parallel, the two polymers show distinct grazing incidence X‐ray scattering spectra indicative of the presence of stacks with different orientation patterns in optimized thin‐film BHJ devices. Independent of the packing pattern the spectroscopic data also reveals the existence of polymer aggregates in the pristine polymer films as well as in both blends which trap excitons and hinder their dissociation.     

Impact of Fullerene on the Photophysics of Ternary Small Molecule Organic Solar Cells

Ternary organic solar cells (OSCs) are among the best‐performing organic photovoltaic devices to date, largely due to the recent development of nonfullerene acceptors. However, fullerene molecules still play an important role in ternary OSC systems, since, for reasons not well understood, they often improve the device performance, despite their lack of absorption. Here, the photophysics of a prototypical ternary small‐molecule OSC blend composed of the donor DR3, the nonfullerene acceptor ICC6, and the fullerene derivative PC₇₁BM is studied by ultrafast spectroscopy. Surprisingly, it is found that after excitation of PC₇₁BM, ultrafast singlet energy transfer to ICC6 competes efficiently with charge transfer. Subsequently, singlets on ICC6 undergo hole transfer to DR3, resulting in free charge generation. Interestingly, PC₇₁BM improves indirectly the electron mobility of the ternary blend, while electrons reside predominantly in ICC6 domains as indicated by fast spectroscopy. The improved mobility facilitates charge carrier extraction, in turn leading to higher device efficiencies of the ternary compared to binary solar cells. Using the (photo)physical parameters obtained from (transient) spectroscopy and charge transport measurements, the device's current–voltage characteristics are simulated and it is demonstrated that the parameters accurately reproduce the experimentally measured device performance.     

Revealing Hidden UV Instabilities in Organic Solar Cells by Correlating Device and Material Stability

With state‐of‐the‐art organic solar cells (OSCs) surpassing 16% efficiency, stability becomes critical for commercialization. In this work, the power of using photoluminescence (PL) measurements on plain films is demonstrated, as well as high‐performance liquid chromatography analysis to reveal the origin of UV instabilities in OSCs based on the most commonly used acceptors PC₇₀BM ([6,6]‐phenyl‐C71‐butyric acid methyl ester), ITIC (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), and o‐IDTBR (indacenodithiophene‐based non‐fullerene acceptor). The UV dependent stability tests reveal instabilities in solar cells based on PC₇₀BM and ITIC while devices based on o‐IDTBR are highly stable even under UV illumination. The analysis of solar cell devices based on charge extraction and sub‐bandgap external quantum efficiency only shows the UV‐dependent emergence of traps, while PL spectra of plain films on glass allows the disentanglement and identification of individual instabilities in multi‐component bulk‐heterojunction devices. In particular, the PL analysis demonstrates UV instabilities of PC₇₀BM and ITIC toward the processing additive 1,8 diiodooctane (DIO). The chemical analysis reveals the in‐depth mechanism, by providing direct proof of photochemical reactions of PC₇₀BM and ITIC with UV‐induced radicals of DIO. Based on this scientific understanding, it is shown how to stabilize PBQ‐QF:PC₇₀BM devices.     

Overcoming Fill Factor Reduction in Ternary Polymer Solar Cells by Matching the Highest Occupied Molecular Orbital Energy Levels of Donor Polymers

Despite the potential of ternary polymer solar cells (PSCs) to improve photocurrents, ternary architecture is not widely utilized for PSCs because its application has been shown to reduce fill factor (FF). In this paper, a novel technique is reported for achieving highly efficient ternary PSCs without this characteristic sharp decrease in FF by matching the highest occupied molecular orbital (HOMO) energy levels of two donor polymers. Our ternary device—made from a blend of wide‐bandgap poly[4,8‐bis(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene‐alt‐2,5‐dioctyl‐4,6‐di(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,3(2H,5H)‐dione) (PBDT‐DPPD) polymer, narrow‐bandgap poly[4,8‐bis[5‐(2‐ethylhexyl)‐2‐thienyl]benzo[1,2‐b:4,5‐b′]dithiophene‐alt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐)‐2‐carboxylate‐2‐ 6‐diyl)] (PTB7‐Th) polymer, and [6,6]‐phenyl C₇₀‐butyric acid methyl ester (PC₇₀BM)—exhibits a maximum power conversion efficiency of 10.42% with an open‐circuit voltage of 0.80 V, a short‐circuit current of 17.61 mA cm^?2, and an FF of 0.74. In addition, this concept is extended to quaternary PSCs made by using three different donor polymers with similar HOMO levels. Interestingly, the quaternary PSCs also yield a good FF (≈0.70)—similar to those of corresponding binary PSCs. This study confirms that the HOMO levels of the polymers used on the photoactive layer of PSCs are a crucial determinant of a high FF.     

Plasmonic Backscattering Effect in High‐Efficient Organic Photovoltaic Devices

A universal strategy for efficient light trapping through the incorporation of gold nanorods on the electron transport layer (rear) of organic photovoltaic devices is demonstrated. Utilizing the photons that are transmitted through the active layer of a bulk heterojunction photovoltaic device and would otherwise be lost, a significant enhancement in power conversion efficiency (PCE) of poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)]:phenyl‐C₇₁‐butyric acid methyl ester (PCDTBT:PC₇₁BM) and 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]] (PTB7):PC₇₁BM by ≈13% and ≈8%, respectively. PCEs over 8% are reported for devices based on the PTB7:PC₇₁BM blend. A comprehensive optical and electrical characterization of our devices to clarify the influence of gold nanorods on exciton generation, dissociation, charge recombination, and transport inside the thin film devices is performed. By correlating the experimental data with detailed numerical simulations, the near‐field and far‐field scattering effects are separated of gold nanorods (Au NRs), and confidently attribute part of the performance enhancement to the enhanced absorption caused by backscattering. While, a secondary contribution from the Au NRs that partially protrude inside the active layer and exhibit strong near‐fields due to localized surface plasmon resonance effects is also observed but is minor in magnitude. Furthermore, another important contribution to the enhanced performance is electrical in nature and comes from the increased charge collection probability.