Efficient Phthalimide Copolymer‐Based Bulk Heterojunction Solar Cells: How the Processing Additive Influences Nanoscale Morphology and Photovoltaic Properties

The power conversion efficiency of poly(N‐(2‐ethylhexyl)‐3,6‐bis(4‐dodecyloxythiophen‐2‐yl)phthalimide) (PhBTEH)/fullerene bulk heterojunction solar cells improves from 0.43 to 4.1% by using a processing additive. The underlying mechanism for the almost 10‐fold enhancement in solar cell performance is found to be inhibition of fullerene intercalation into the polymer side chains and regulation of the relative crystallization/aggregation rates of the polymer and fullerene. An optimal interconnected two‐phase morphology with 15–20 nm domains is obtained when a processing additive is used compared with 100–300 nm domains without the additive. The results demonstrate that a processing additive provides an effective means of controlling both the fullerene intercalation in polymer/fullerene blends and the domain sizes of their phase‐separated nanoscale morphology.     

Non‐Fullerene Acceptor‐Based Bulk Heterojunction Polymer Solar Cells: Engineering the Nanomorphology via Processing Additives

The performance of bulk heterojunction solar cells made from blends of a non‐fullerene acceptor, N,N′‐bis(2‐ethylhexyl)‐2,6‐bis(5″‐hexyl‐[2,2′;5′,2″]terthiophen‐5yl)‐1,4,5,8‐naphthalene diimide (NDI‐3TH), and poly(3‐hexylthiophene) (P3HT) donor is enhanced 10‐fold by using a processing additive in conjunction with an electron‐blocking and a hole‐blocking buffer layers. The power conversion efficiency of P3HT:NDI‐3TH solar cells improves from 0.14% to 1.5% by using a processing additive (1,8‐diiodooctane) at an optimum concentration of 0.2 vol%, which is far below the 2‐3 vol% optimum concentrations found in polymer/fullerene systems. TEM and AFM imaging show that the size and connectivity of the NDI‐3TH domains in the phase‐separated P3HT:NDI‐3TH blends vary strongly with the concentration of the processing additive. These results demonstrate, for the first time, that processing additives can be effective in the optimization of the morphology and performance of bulk heterojunction polymer solar cells based on non‐fullerene acceptors.     

Controlling Solution‐Phase Polymer Aggregation with Molecular Weight and Solvent Additives to Optimize Polymer‐Fullerene Bulk Heterojunction Solar Cells

The bulk heterojunction (BHJ) solar cell performance of many polymers depends on the polymer molecular weight (M _n) and the solvent additive(s) used for solution processing. However, the mechanism that causes these dependencies is not well understood. This work determines how M _n and solvent additives affect the performance of BHJ solar cells made with the polymer poly(di(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene‐co‐octylthieno[3,4‐c]pyrrole‐4,6‐dione) (PBDTTPD). Low M _n PBDTTPD devices have exceedingly large fullerene‐rich domains, which cause extensive charge‐carrier recombination. Increasing the M _n of PBDTTPD decreases the size of these domains and significantly improves device performance. PBDTTPD aggregation in solution affects the size of the fullerene‐rich domains and this effect is linked to the dependency of PBDTTPD solubility on M _n. Due to its poor solubility high M _n PBDTTPD quickly forms a fibrillar polymer network during spin‐casting and this network acts as a template that prevents large‐scale phase separation. Furthermore, processing low M _n PBDTTPD devices with a solvent additive improves device performance by inducing polymer aggregation in solution and preventing large fullerene‐rich domains from forming. These findings highlight that polymer aggregation in solution plays a significant role in determining the morphology and performance of BHJ solar cells.     

Linking Vertical Bulk‐Heterojunction Composition and Transient Photocurrent Dynamics in Organic Solar Cells with Solution‐Processed MoOx Contact Layers

It is demonstrated that a combination of microsecond transient photocurrent measurements and film morphology characterization can be used to identify a charge‐carrier blocking layer within polymer:fullerene bulk‐heterojunction solar cells. Solution‐processed molybdenum oxide (s‐MoO_x) interlayers are used to control the morphology of the bulk‐heterojunction. By selecting either a low‐ or high‐temperature annealing (70 °C or 150 °C) for the s‐MoO_x layer, a well‐performing device is fabricated with an ideally interconnected, high‐efficiency morphology, or a device is fabricated in which the fullerene phase segregates near the hole extracting contact preventing efficient charge extraction. By probing the photocurrent dynamics of these two contrasting model systems as a function of excitation voltage and light intensity, the optoelectronic responses of the solar cells are correlated with the vertical phase composition of the polymer:fullerene active layer, which is known from dynamic secondary‐ion mass spectroscopy (DSIMS). Numerical simulations are used to verify and understand the experimental results. The result is a method to detect poor morphologies in operating organic 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.     

Overcoming the “Light‐Soaking” Issue in Inverted Organic Solar Cells by the Use of Al:ZnO Electron Extraction Layers

A common phenomenon of organic solar cells (OSCs) incorporating metal‐oxide electron extraction layers is the requirement to expose the devices to UV light in order to improve device characteristics – known as the so‐called “light‐soaking” issue. This behaviour appears to be of general validity for various metal‐oxide layers, various organic donor/acceptor systems, and regardless if single junction devices or multi stacked cells are considered. The requirement of UV exposure of OSCs may impose severe problems if substrates with limited UV transmission, UV blocking filters or UV to VIS down‐conversion concepts are applied. In this paper, we will demonstrate that this issue can be overcome by the use of Al doped ZnO (AZO) as electron extraction interlayer. In contrast to devices based on TiO_x and ZnO, the AZO devices show well‐behaved solar cell characteristics with a high fill factor (FF) and power conversion efficiency (PCE) even without the UV spectral components of the AM1.5 solar spectrum. As opposed to previous claims, our results indicate that the origin of s‐shaped characteristics of the OSCs is the metal‐oxide/organic interface. The electronic structures of the TiO_x/fullerene and AZO/fullerene interfaces are studied by photoelectron spectroscopy, revealing an electron extraction barrier for the TiO_x/fullerene case and facilitated electron extraction for AZO/fullerene. These results are of general relevance for organic solar cells based on various donor acceptor active systems.     

Mixed Domains Enhance Charge Generation and Extraction in Bulk‐Heterojunction Solar Cells with Small‐Molecule Donors

The interplay between nanomorphology and efficiency of polymer‐fullerene bulk‐heterojunction (BHJ) solar cells has been the subject of intense research, but the generality of these concepts for small‐molecule (SM) BHJs remains unclear. Here, the relation between performance; charge generation, recombination, and extraction dynamics; and nanomorphology achievable with two SM donors benzo[1,2‐b:4,5‐b]dithiophene‐pyrido[3,4‐b]‐pyrazine BDT(PPTh₂)₂, namely SM1 and SM2, differing by their side‐chains, are examined as a function of solution additive composition. The results show that the additive 1,8‐diiodooctane acts as a plasticizer in the blends, increases domain size, and promotes ordering/crystallinity. Surprisingly, the system with high domain purity (SM1) exhibits both poor exciton harvesting and severe charge trapping, alleviated only slightly with increased crystallinity. In contrast, the system consisting of mixed domains and lower crystallinity (SM2) shows both excellent exciton harvesting and low charge recombination losses. Importantly, the onset of large, pure crystallites in the latter (SM2) system reduces efficiency, pointing to possible differences in the ideal morphologies for SM‐based BHJ solar cells compared with polymer‐fullerene devices. In polymer‐based systems, tie chains between pure polymer crystals establish a continuous charge transport network, whereas SM‐based active layers may in some cases require mixed domains that enable both aggregation and charge percolation to the electrodes.     

Non‐invasive optical method for real‐time assessment of intracorneal riboflavin concentration and efficacy of corneal cross‐linking

Keratoconus is the primary cause of corneal transplantation in young adults worldwide. Riboflavin/UV‐A corneal cross‐linking may effectively halt the progression of keratoconus if an adequate amount of riboflavin enriches the corneal stroma and is photo‐oxidated by UV‐A light for generating additional cross‐linking bonds between stromal proteins and strengthening the biomechanics of the weakened cornea. Here we reported an UV‐A theranostic prototype device for performing corneal cross‐linking with the ability to assess corneal intrastromal concentration of riboflavin and to estimate treatment efficacy in real time. Seventeen human donor corneas were treated according to the conventional riboflavin/UV‐A corneal cross‐linking protocol. Ten of these tissues were probed with atomic force microscopy in order to correlate the intrastromal riboflavin concentration recorded during treatment with the increase in elastic modulus of the anterior corneal stroma. The intrastromal riboflavin concentration and its consumption during UV‐A irradiation of the cornea were highly significantly correlated (R = 0.79; P = .03) with the treatment‐induced stromal stiffening effect. The present study showed an ophthalmic device that provided an innovative, non‐invasive, real‐time monitoring solution for estimating corneal cross‐linking treatment efficacy on a personalized basis.      

Thieno[3,4‐c]Pyrrole‐4,6‐Dione‐Based Polymer Acceptors for High Open‐Circuit Voltage All‐Polymer Solar Cells

While polymer acceptors are promising fullerene alternatives in the fabrication of efficient bulk heterojunction (BHJ) solar cells, the range of efficient material systems relevant to the “all‐polymer” BHJ concept remains narrow, and currently limits the perspectives to meet the 10% efficiency threshold in all‐polymer solar cells. This report examines two polymer acceptor analogs composed of thieno[3,4‐c ]pyrrole‐4,6‐dione (TPD) and 3,4‐difluorothiophene ([2F]T) motifs, and their BHJ solar cell performance pattern with a low‐bandgap polymer donor commonly used with fullerenes (PBDT‐TS1; taken as a model system). In this material set, the introduction of a third electron‐deficient motif, namely 2,1,3‐benzothiadiazole (BT), is shown to (i) significantly narrow the optical gap (E _opt) of the corresponding polymer (by ≈0.2 eV) and (ii) improve the electron mobility of the polymer by over two orders of magnitude in BHJ solar cells. In turn, the narrow‐gap P2TPDBT[2F]T analog (E _opt = 1.7 eV) used as fullerene alternative yields high open‐circuit voltages (V _OC) of ≈1.0 V, notable short‐circuit current values (J _SC) of ≈11.0 mA cm⁻², and power conversion efficiencies (PCEs) nearing 5% in all‐polymer BHJ solar cells. P2TPDBT[2F]T paves the way to a new, promising class of polymer acceptor candidates.     

A Series of Pyrene‐Substituted Silicon Phthalocyanines as Near‐IR Sensitizers in Organic Ternary Solar Cells

An attractive method to broaden the absorption bandwidth of polymer/fullerene‐based bulk heterojunction (BHJ) solar cells is to blend near infrared (near‐IR) sensitizers into the host system. Axial substitution of silicon phthalocyanines (Pcs) opens a possibility to modify the chemical, thermodynamic, electronic, and optical properties. Different axial substitutions are already designed to modify the thermodynamic properties of Pcs, but the impact of extending the π‐conjugation of the axial ligand on the opto‐electronic properties, as a function of the length of the alkyl spacer, has not been investigated yet. For this purpose, a novel series of pyrene‐substituted silicon phthalocyanines (SiPc‐Pys) with varying lengths of alkyl chain tethers are synthesized. The UV–vis and external quantum efficiency (EQE) results exhibit an efficient near IR sensitization up to 800 nm, clearly establishing the impact of the pyrene substitution. This yields an increase of over 20% in the short circuit current density (J _SC) and over 50% in the power conversion efficiency (PCE) for the dye‐sensitized ternary device. Charge generation, transport properties, and microstructure are studied using different advanced technologies. Remarkably, these results provide guidance for the diverse and judicious selection of dye sensitizers to overcome the absorption limitation and achieve high efficiency ternary solar cells.     

Absolute Measurement of Domain Composition and Nanoscale Size Distribution Explains Performance in PTB7:PC71BM Solar Cells

The importance of morphology to organic solar cell performance is well known, but to date, the lack of quantitative, nanoscale and statistical morphological information has hindered obtaining direct links to device function. Here resonant X‐ray scattering and microscopy are combined to quantitatively measure the nanoscale domain size, distribution and composition in high efficiency solar cells based on PTB7 and PC₇₁BM. The results show that the solvent additive diiodooctane dramatically shrinks the domain size of pure fullerene agglomerates that are embedded in a polymer‐rich 70/30 wt.% molecularly mixed matrix, while preserving the domain composition relative to additive‐free devices. The fundamental miscibility between the species – measured to be equal to the device's matrix composition – is likely the dominant factor behind the overall morphology with the additive affecting the dispersion of excess fullerene. As even the molecular ordering measured by X‐ray diffraction is unchanged between the two processing routes the change in the distribution of domain size and therefore increased domain interface is primarily responsible for the dramatic increase in device performance. While fullerene exciton harvesting is clearly one significant cause of the increase owing to smaller domains, a measured increase in harvesting from the polymer species indicates that the molecular mixing is not the reason for the high efficiency in this system. Rather, excitations in the polymer likely require proximity to a pure fullerene phase for efficient charge separation and transport. Furthermore, in contrast to previous measurements on a PTB7‐based system, a hierarchical morphology was not observed, indicating that it is not necessary for high performance.     

Enhanced Uniformity and Area Scaling in Carbon Nanotube–Fullerene Bulk‐Heterojunction Solar Cells Enabled by Solvent Additives

Single‐walled carbon nanotube (SWCNT) fullerene solar cells have recently attracted attention due to their low‐cost processing, high environmental stability, and near‐infrared absorption. While SWCNT–fullerene bulk‐heterojunction photovoltaics employing an inverted architecture and polychiral SWCNTs have achieved efficiencies exceeding 3% over device areas of ≈1 mm², large‐area SWCNT solar cells have not yet been demonstrated. In particular, with increasing device area, spatial inhomogeneities in the SWCNT film have limited overall device performance. Here, 1,8‐diiodooctane (DIO) is utilized as a solvent additive to reduce fullerene domain size and to improve SWCNT–fullerene bulk‐heterojunction morphology. Under optimized conditions, DIO elucidates the influence of SWCNT chiral distribution on overall device performance, revealing a tradeoff between short‐circuit current density and fill factor as a function of the chirality distribution present. The combination of SWCNT chirality distribution engineering and improved spatial homogeneity via solvent additives enables area‐scaling of SWCNT–fullerene solar cells with performance comparable to small‐area cells.     

Efficiency Enhancement of Polymer Solar Cells Based on Poly(3‐hexylthiophene)/Indene‐C70 Bisadduct via Methylthiophene Additive

Photovoltaic performance of polymer solar cells based on poly(3‐hexylthiophene) (P3HT) as the donor and indene‐C₇₀ bisadduct (IC₇₀BA) as the acceptor is improved by adding 3 vol% 3‐methylthiophene (MT) or 3‐hexylthiophene (HT) as processing additives. The results of UV‐vis absorption spectroscopy, X‐ray diffraction analysis and atomic force microscopy indicate that with the MT or HT processing additive, the active layer of the blend of P3HT/IC₇₀BA showed strengthened absorbance, enhanced crystallinity and improved film morphology. The power conversion efficiency (PCE) of the PSCs was improved from 5.80% for the device without the additive to 6.35% for the device with HT additive and to 6.69% with MT additive. The PCE of 6.69% is the top value reported so far for the PSCs based on P3HT.     

Polymer Doping for High‐Efficiency Perovskite Solar Cells with Improved Moisture Stability

Each component layer in a perovskite solar cell plays an important role in the cell performance. Here, a few types of polymers including representative p‐type and n‐type semiconductors, and a classical insulator, are chosen to dope into a perovskite film. The long‐chain polymer helps to form a network among the perovskite crystalline grains, as witnessed by the improved film morphology and device stability. The dewetting process is greatly suppressed by the cross‐linking effect of the polymer chains, thereby resulting in uniform perovskite films with large grain sizes. Moreover, it is found that the polymer‐doped perovskite shows a reduced trap‐state density, likely due to the polymer effectively passivating the perovskite grain surface. Meanwhile the doped polymer formed a bridge between grains for efficient charge transport. Using this approach, the solar cell efficiency is improved from 17.43% to as high as 19.19%, with a much improved stability. As it is not required for the polymer to have a strict energy level matching with the perovskite, in principle, one may use a variety of polymers for this type of device design.     

Toward High‐Temperature Stability of PTB7‐Based Bulk Heterojunction Solar Cells: Impact of Fullerene Size and Solvent Additive

The use of fullerene as acceptor limits the thermal stability of organic solar cells at high temperatures as their diffusion inside the donor leads to phase separation via Ostwald ripening. Here it is reported that fullerene diffusion is fully suppressed at temperatures up to 140 °C in bulk heterojunctions based on the benzodithiophene‐based polymer (the 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) in combination with the fullerene derivative [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC₇₀BM). The blend stability is found independently of the presence of diiodooctane (DIO) used to optimize nanostructuration and in contrast to PTB7 blends using the smaller fullerene derivative PC₇₀BM. The unprecedented thermal stability of PTB7:PC₇₀BM layers is addressed to local minima in the mixing enthalpy of the blend forming stable phases that inhibit fullerene diffusion. Importantly, although the nanoscale morphology of DIO processed blends is thermally stable, corresponding devices show strong performance losses under thermal stress. Only by the use of a high temperature annealing step removing residual DIO from the device, remarkably stable high efficiency solar cells with performance losses less than 10% after a continuous annealing at 140 °C over 3 days are obtained. These results pave the way toward high temperature stable polymer solar cells using fullerene acceptors.     

Burn‐in Free Nonfullerene‐Based Organic Solar Cells

Organic solar cells that are free of burn‐in, the commonly observed rapid performance loss under light, are presented. The solar cells are based on poly(3‐hexylthiophene) (P3HT) with varying molecular weights and a nonfullerene acceptor (rhodanine‐benzothiadiazole‐coupled indacenodithiophene, IDTBR) and are fabricated in air. P3HT:IDTBR solar cells light‐soaked over the course of 2000 h lose about 5% of power conversion efficiency (PCE), in stark contrast to [6,6]‐Phenyl C61 butyric acid methyl ester (PCBM)‐based solar cells whose PCE shows a burn‐in that extends over several hundreds of hours and levels off at a loss of ≈34%. Replacing PCBM with IDTBR prevents short‐circuit current losses due to fullerene dimerization and inhibits disorder‐induced open‐circuit voltage losses, indicating a very robust device operation that is insensitive to defect states. Small losses in fill factor over time are proposed to originate from polymer or interface defects. Finally, the combination of enhanced efficiency and stability in P3HT:IDTBR increases the lifetime energy yield by more than a factor of 10 when compared with the same type of devices using a fullerene‐based acceptor instead.     

Physically Stable Polymer‐Membrane Electrolytes for Highly Efficient Solid‐State Dye‐Sensitized Solar Cells with Long‐Term Stability

A 3D polymer‐network‐membrane (3D‐PNM) electrolyte is described for highly stable, solid‐state dye‐sensitized solar cells (DSCs) with excellent power‐conversion efficiency (PCE). The 3D‐PNM electrolyte is prepared by using one‐pot in situ cross‐linking polymerization on the surface of dye‐sensitized TiO₂ particles in the presence of redox species. This method allows the direct connection of the 3D‐PNM to the surface of the TiO₂ particles as well as the in situ preparation of the electrolyte gel during device assembly. There are two junction areas (liquid and solid‐state junctions) in the DSCs that employ conventional polymer electrolytes, and the major interface is at the liquid‐state junction. The solid‐state junction is dominant in the DSCs that employ the 3D‐PNM electrolyte, which exhibit almost constant performance during aging at 65 °C for over 700 h (17.0 to 17.2 mA cm^–2). The best cell performance gives a PCE of 9.1%; this is slightly better than the performance of a DSC that employs a liquid electrolyte.     

Crosslinkable Amino‐Functionalized Conjugated Polymer as Cathode Interlayer for Efficient Inverted Polymer Solar Cells

A novel crosslinkable aminoalkyl‐functionalized polymer, poly[9,9‐bis(6‐(N,N‐diethylamino)propyl)fluorene‐alt‐9,9‐bis(hex‐5‐en‐1‐yl)‐fluorene] (PFN‐V), is designed and synthesized. The resulting polymer can be rapidly crosslinked by UV‐curing within 5 s in a nearly quantitative yield based on the “click” chemistry of alkyene end‐groups of the PFN‐V side chains and the addition of 1,8‐octanedithiol. The crosslinked PFN‐V film exhibits excellent solvent resistance property and can act as effective cathode interlayer to modify the indium tin oxide (ITO) electrode, which can thus facilitate the formation of Ohmic contact between cathode and active layer. The surface energy of PFN‐V is quite comparable to that of PC₇₁BM, which is favorable for the formation of vertical phase separation in the bulk heterojunction film that can facilitate extraction of charges as verified by transient photocurrent measurements. Based on the resulting PFN‐V as the cathode interlayer, the fabricated polymer solar cells with inverted device structure show a remarkable enhancement of power conversion efficiency from 3.11% for the control device to 9.18% for PFN‐V based device. These observations indicate that the synthesized PFN‐V can be a promising crosslinked copolymer as the cathode interlayer for high performance polymer solar cells.     

Effect of Processing Additives on the Solidification of Blade‐Coated Polymer/Fullerene Blend Films via In‐Situ Structure Measurements

The use of processing additives has emerged as a powerful approach for the optimization of active layer performance in organic photovoltaic devices. However, definitive physical mechanisms explaining the impact of additives have not yet been determined. To elucidate the role of additives, we have studied the time evolution of structure in polymer‐fullerene films blade‐coated from additive containing solutions using in‐situ spectroscopic ellipsometry and UV–vis transmission. Additives that are poor solvents for poly(3‐hexylthiophene) (P3HT), such as 1,8‐octanedithiol, and additives that are good solvents for P3HT, such as 1‐chloronapthalene, both promote improved polymer order, phase segregation, and device performance. Regardless of the presence or type of additive, the polymer order develops under conditions of extreme supersaturation. Additives, regardless of whether they are solvents for P3HT, promote earlier polymer aggregation compared to additive ‐ free solutions presumably by degrading the solvent quality. We find evidence that the details of the final film morphology may be linked to the influence of the substrate and long‐time film plasticization in the cases of the non‐solvent and solvent respectively.     

Imidazolium‐Substituted Polythiophenes as Efficient Electron Transport Materials Improving Photovoltaic Performance

In the field of polymer solar cells, improving photovoltaic performance has been the main driver over the past decade. To achieve high power conversion efficiencies, a plethora of new photoactive donor polymers and fullerene derivatives have been developed and blended together in bulk heterojunction active layers. Simultaneously, further optimization of the device architecture is also of major importance. In this respect, we report on the use of specific types of electron transport layers to boost the inherent I–V properties of polymer solar cell devices, resulting in a considerable gain in overall photovoltaic output. Imidazolium‐substituted polythiophenes are introduced as appealing electron transport materials, outperforming the currently available analogous conjugated polyelectrolytes, mainly by an increase in short‐circuit current. The molecular weight of the ionic polythiophenes has been identified as a crucial parameter influencing performance.