Charge Density Dependent Nongeminate Recombination in Organic Bulk Heterojunction Solar Cells

Apparent recombination orders exceeding the value of two expected for bimolecular recombination have been reported for organic solar cells in various publications. Two prominent explanations are bimolecular losses with a carrier concentration dependent prefactor due to a trapping limited mobility and protection of trapped charge carriers from recombination by a donor–acceptor phase separation until re‐emission from these deep states. In order to clarify which mechanism is dominant temperature‐ and illumination‐dependent charge extraction measurements are performed under open circuit and short circuit conditions at poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C₆₁ butyric acid methyl ester (P3HT:PC₆₁BM) and PTB7:PC₇₁BM (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]]) solar cells in combination with current–voltage characteristics. It is shown that the charge carrier density n dependence of the mobility μ and the recombination prefactor are different for P3HT:PC₆₁BM at temperatures below 300 K and PTB7:PC₇₁BM at room temperature. Therefore, in addition to μ(n), a detrapping limited recombination in systems with at least partial donor–acceptor phase separation is required to explain the high recombination orders.     

A universal roll‐to‐roll slot‐die coating approach towards high‐efficiency organic photovoltaics

This work develops a combinational use of solvent additive and in‐line drying oven on the flexible organic photovoltaics to improve large‐area roll‐to‐roll (R2R) slot‐die coating process. Herein, addition of 1,8‐diiodooctane (DIO) in the photoactive layer is conducted to yield a performance of 3.05% based on the blending of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PC₆₁BM), and a very promising device performance of 7.32% based on the blending of 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) and [6,6]‐phenyl C₇₁‐butyric acid methyl ester (PC₇₁BM). Based on this R2R slot‐die coating approach for various polymers, we demonstrate the high‐performance result with respect to the up‐scaling from small high‐PCE cell to large‐area module. This present study provides a route for fabricating a low‐cost, large‐area, and environmental‐friendly flexible organic photovoltaics.     

A Versatile Fluoro‐Containing Low‐Bandgap Polymer for Efficient Semitransparent and Tandem Polymer Solar Cells

The versatility of a fluoro‐containing low band‐gap 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) in organic photovoltaics (OPVs) applications is demonstrated. High boiling point 1,3,5‐trichlorobenzene (TCB) is used as a solvent to manipulate PCPDTFBT:[6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) active layer morphology to obtain high‐performance single‐junction devices. It promotes the crystallization of PCPDTFBT polymer, thus improving the charge‐transport properties of the active layer. By combining the morphological manipulation with interfacial optimization and device engineering, the single‐junction device exhibits both good air stability and high power‐conversion efficiency (PCE, of 6.6%). This represents one of the highest PCE values for cyclopenta[2,1‐b;3,4‐b’]dithiophene (CPDT)‐based OPVs. This polymer is also utilized for constructing semitransparent solar cells and double‐junction tandem solar cells to demonstrate high PCEs of 5.0% and 8.2%, respectively.     

Cubic‐Like Bimolecular Crystal Evolution and over 12% Efficiency in Halogen‐Free Ternary Solar Cells

In this study, the solubility properties of a given ternary blend set, with two donors (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 (PTB7‐Th) and benzo[1,2‐b;4,5‐b′]dithiophene‐based small molecule (DR3TSBDT)) and one acceptor ([6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM)), in a series of solvents are determined, and active material–solvent interactions are used as an aid for finding suitable nonchlorinated solvents to achieve effective ternary organic solar cells (OSCs) based on PTB7‐Th:DR3TSBDT:PC₇₁BM. An exceptional power conversion efficiency (PCE) as high as 12.3% (certified 11.94%) is obtained using the developed nonhalogenated processing system. In‐depth investigations (morphology, charge mobility, recombination dynamics, and OSC characteristics) uncover the underlying structure–property relationships as a function of the chosen nonhalogenated systems. Another intriguing finding of this study is the formation of a cubic bimolecular crystal structure of PTB7‐Th:PC₇₁BM in a nonhalogenated system, which is the first such demonstration in blend films. This sheds light upon the fact that the physical properties of a material applied from different solutions may surpass the variation in the properties between two material having totally different molecular structure. Therefore, this work not only offers important scientific insights into developing highly efficient and eco‐friendly OSCs but also improves our understanding of achievable bimolecular crystals with an intercalated structure.     

Optimization of the Power Conversion Efficiency of Room Temperature‐Fabricated Polymer Solar Cells Utilizing Solution Processed Tungsten Oxide and Conjugated Polyelectrolyte as Electrode Interlayer

The utilization of a conjugated polyelectrolyte‐ionic liquid crystal (CPE‐ILC) complex as electron transporting layer (ETL) to improve the compatibility between the ITO and hydrophobic active layer and to promote the dipole orientation at cathode interface is reported. Simultaneously, a hole transporting layer (HTL) of solution processed tungsten oxide together with poly(2,6‐bis(trimethyltin)‐4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐alt‐4,6‐Dibromo‐thieno[3,4‐b]thiophene‐2‐carboxylic acid 2‐[2‐(2‐methoxy‐ethoxy)‐ethoxy]‐ethyl ester) (PBDTT‐TT‐TEG) efficiently shifts the work function of Ag electrode in this device. The interfacial modification of these interlayers achieves energy alignment at both electrodes. The power conversion efficiency (PCE) of the PSC based on ITO/PFN‐CbpSO/PBDTTT‐C‐T:PC₇₀BM/PBDTT‐TT‐TEG/WO₃/Ag with solution processed interlayers reaches to 7.8%. It is worthy to note that except for the electrodes, all layers of device are fabricated by solution process at room temperature and without annealing. In the case of incorporating ZnO layer into this device, the device efficiency further increases to 8.5%, which is the best value reported from PBDTTT‐C‐T:PC₇₀BM‐based solar cells with solution processed interlayers at both electrodes so far.     

The effect of processing solvent dependent film aggregation on the photovoltaic performance of squaraine:PC71BM bulk heterojunction solar cells

In this work, we systemically investigated the processing solvent-dependent aggregation behavior of a squaraine dye, 2,4-bis[4-(N,N-dibutylamino)-2,6- dihydroxyphenyl] squaraine (DBSQ), in a DBSQ: [6,6]-phenyl-C71-butyric acid methyl ester (PC₇₁BM) blend film, as well as the aggregation effect on the photovoltaic performance of DBSQ:PC₇₁BM bulk heterojunctions (BHJs). Our finding shows that the aggregation behavior of DBSQ dye in the blend film can be controlled via the proper selection of the processing solvents. For a J-aggregate (head-to-tail molecule alignment) DBSQ:PC₇₁BM active layer based BHJ cells, a power conversion efficiency (PCE) of over 5% can be obtained, which is 75% higher than that of the H-aggregate (parallel molecule packing) active layer based BHJ cells. Our results indicate that the processing solvent controlled J-aggregation formation shall be considered as effective approach to tune the optical and electrical properties of thin films for high-performance BHJ solar cells.     

Photoinduced Hole Transfer Becomes Suppressed with Diminished Driving Force in Polymer‐Fullerene Solar Cells While Electron Transfer Remains Active

Device performance and photoinduced charge transfer are studied in donor/acceptor blends of the oxidation‐resistant conjugated polymer poly[(4,8‐bis(2‐hexyldecyl)oxy)benzo[1,2‐b:4,5‐b′]dithiophene)‐2,6‐diyl‐alt‐(2,5‐bis(3‐dodecylthiophen‐2‐yl)benzo[1,2‐d;4,5‐d′]bisthiazole)] (PBTHDDT) with the following fullerene acceptors: [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM); [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM); and the indene‐C₆₀ bis‐adduct IC₆₀BA). Power conversion efficiency improves from 1.52% in IC₆₀BA‐based solar cells to 3.75% in PC₇₁BM‐based devices. Photoinduced absorption (PIA) of the PBTHDDT:fullerene blends suggests that exciting the donor polymer leads to long‐lived positive polarons on the polymer and negative polarons on the fullerene in all three polymer fullerene blends. Selective excitation of the fullerene in PC₇₁BM or PC₆₁BM blends also generates long‐lived polarons. In contrast, no discernible PIA features are observed when selectively exciting the fullerene in a PBTHDDT/IC₆₀BA blend. A relatively small driving force of ca. 70 meV appears to sustain charge separation via photoinduced hole transfer from photoexcited PC₆₁BM to the polymer. The decreased driving force for photoinduced hole transfer in the IC₆₀BA blend effectively turns off hole transfer from IC₆₀BA excitons to the host polymer, even while electron transfer from the polymer to the IC₆₀BA remains active. Suppressed hole transfer from fullerene excitons is a potentially important consideration for materials design and device engineering of organic solar cells.     

Alternating Copolymers of Cyclopenta[2,1‐b;3,4‐b′]dithiophene and Thieno[3,4‐c]pyrrole‐4,6‐dione for High‐Performance Polymer Solar Cells

A series of alternating copolymers of cyclopenta[2,1‐b;3,4‐b′]dithiophene (CPDT) and thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) have been prepared and characterized for polymer solar cell (PSC) applications. Different alkyl side chains, including butyl (Bu), hexyl (He), octyl (Oc), and 2‐ethylhexyl (EH), are introduced to the TPD unit in order to adjust the packing of the polymer chain in the solid state, while the hexyl side chain on the CPDT unit remains unchanged to simplify discussion. The polymers in this series have a simple main chain structure and can be synthesized easily, have a narrow band gap and a broad light absorption. The different alkyl chains on the TPD unit not only significantly influence the solubility and chain packing, but also fine tune the energy levels of the polymers. The polymers with Oc or EH group have lower HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energy levels, resulting higher open circuit voltages (V_oc) of the PSC devices. Power conversion efficiencies (PCEs) up to 5.5% and 6.4% are obtained from the devices of the Oc substituted polymer (PCPDTTPD‐Oc) with PC₆₁BM and PC₇₁BM, respectively. This side chain effect on the PSC performance is related to the formation of a fine bulk heterojunction structure of polymer and PCBM domains, as observed with atomic force microscopy.     

Influence of Phase Segregation on Recombination Dynamics in Organic Bulk‐Heterojunction Solar Cells

The recombination dynamics of charge carriers in organic bulk‐heterojunction (BHJ) solar cells made of the blend system poly(2,5‐bis(3‐dodecylthiophen‐2‐yl)thieno[2,3‐b]thiophene) (pBTCT‐C₁₂):[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) with a donor–acceptor ratio of 1:1 and 1:4 are studied here. The techniques of charge‐carrier extraction by linearly increasing voltage (photo‐CELIV) and, as local probe, time‐resolved microwave conductivity are used. A difference of one order of magnitude is observed between the two blends in the initially extracted charge‐carrier concentration in the photo‐CELIV experiment, which can be assigned to an enhanced geminate recombination that arises through a fine interpenetrating network with isolated phase regions in the 1:1 pBTCT‐C₁₂:PC₆₁BM BHJ solar cells. In contrast, extensive phase segregation in 1:4 blend devices leads to an efficient polaron generation that results in an increased short‐circuit current density of the solar cells. For both studied ratios a bimolecular recombination of polarons is found using the complementary experiments. The charge‐carrier decay order of above two for temperatures below 300 K can be explained on the basis of a release of trapped charges. This mechanism leads to delayed bimolecular recombination processes. The experimental findings can be generalized to all polymer:fullerene blend systems allowing for phase segregation.     

Synthesis of a Modified PC70BM and Its Application as an Electron Acceptor with Poly(3‐hexylthiophene) as an Electron Donor for Efficient Bulk Heterojunction Solar Cells

A simple and effective modification of phenyl‐C₇₀‐butyric acid methyl ester (PC₇₀BM) is carried out in a single step after which the material is used as electron acceptor for bulk heterojunction polymer solar cells (PSCs). The modified PC₇₀BM, namely CN‐PC₇₀BM, showed broader and stronger absorption in the visible region (350–550 nm) of the solar spectrum than PC₇₀BM because of the presence of a cyanovinylene 4‐nitrophenyl segment. The lowest unoccupied molecular energy level (LUMO) of CN‐PC₇₀BM is higher than that of PC₇₀BM by 0.15 eV. The PSC based on the blend (cast from tetrahydrofuran (THF) solution) consists of P3HT as the electron donor and CN‐PC₇₀BM as the electron acceptor and shows a power conversion efficiency (PCE) of 4.88%, which is higher than that of devices based on PC₇₀BM as the electron acceptor (3.23%). The higher PCE of the solar cell based on P3HT:CN‐PC₇₀BM is related to the increase in both the short circuit current (J_sc) and the open circuit voltage (V_oc). The increase in J_sc is related to the stronger light absorption of CN‐PC₇₀BM in the visible region of the solar spectrum as compared to that of PC₇₀BM. In other words, more excitons are generated in the bulk heterojunction (BHJ) active layer. On the other hand, the higher difference between the LUMO of CN‐PC₇₀BM and the HOMO of P3HT causes an enhancement in the V_oc. The addition of 2% (v/v) 1‐chloronapthalene (CN) to the THF solvent during film deposition results in an overall improvement of the PCE up to 5.83%. This improvement in PCE can be attributed to the enhanced crystallinity of the blend (particularly of P3HT) and more balanced charge transport in the device.     

Formation of charge‐transfer complexes significantly improves the performance of polymer solar cells based on PBDTTT‐C‐T: PC71BM

By adding appropriate proportions of nitrobenzene (C₆H₅NO₂) to the blended solution of poly{[4,8‐bis‐(2‐ethyl‐hexyl‐thiophene‐5‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl]‐alt‐[2‐(2′‐ethyl‐hexanoyl)‐thieno[3,4‐b]thiophen‐4,6‐diyl]}:[6,6]‐phenyl‐C71‐butyric acid methyl ester (PBDTTT‐C‐T: PC₇₁BM), we substantially improved the power conversion efficiency from the best reported value of 7.48–8.88%. Experiments and simulations show that nitrobenzene and PBDTTT‐C‐T form stable coplanar charge‐transfer complexes through hydrogen bonds. Formation of the PBDTTT‐C‐T‐C₆H₅NO₂ complex simultaneously increases the external quantum efficiency. The underlying mechanisms of increased external quantum efficiency are attributed to the following: (i) higher lowest unoccupied molecular orbital (LUMO) of PBDTTT‐C‐T‐C₆H₅NO₂ for more efficient photoinduced electron transfer to the LUMO of PC₇₁BM and (ii) efficient quenching of fluorescence in the active layers due to formation of the PBDTTT‐C‐T‐C₆H₅NO₂ complex. This discovery clearly illustrates the potential of hydrogen‐bonded complexes as a new route for efficient polymer‐based photovoltaic devices. Copyright © 2014 John Wiley & Sons, Ltd.     

Donor and Acceptor Unit Sequences Influence Material Performance in Benzo[1,2‐b:4,5‐b′]dithiophene–6,7‐Difluoroquinoxaline Small Molecule Donors for BHJ Solar Cells

Well‐defined small molecule (SM) donors can be used as alternatives to π‐conjugated polymers in bulk‐heterojunction (BHJ) solar cells with fullerene acceptors (e.g., PC₆₁/₇₁BM). Taking advantage of their synthetic tunability, combinations of various donor and acceptor motifs can lead to a wide range of optical, electronic, and self‐assembling properties that, in turn, may impact material performance in BHJ solar cells. In this report, it is shown that changing the sequence of donor and acceptor units along the π‐extended backbone of benzo[1,2‐b:4,5‐b′]dithiophene–6,7‐difluoroquinoxaline SM donors critically impacts (i) molecular packing, (ii) propensity to order and preferential aggregate orientations in thin‐films, and (iii) charge transport in BHJ solar cells. In these systems ( SM1‐3 ), it is found that 6,7‐difluoroquinoxaline ([2F]Q) motifs directly appended to the central benzo[1,2‐b:4,5‐b′]dithiophene (BDT) unit yield a lower‐bandgap analogue ( SM1 ) with favorable molecular packing and aggregation patterns in thin films, and optimized BHJ solar cell efficiencies of ≈6.6%. ¹H‐¹H DQ‐SQ NMR analyses indicate that SM1 and its counterpart with [2F]Q motifs substituted as end‐group SM3 possess distinct self‐assembly patterns, correlating with the significant charge transport and BHJ device efficiency differences observed for the two analogous SM donors (avg. 6.3% vs 2.0%, respectively).     

Efficiency enhancement of polymer solar cells by applying an alcohol-soluble fullerene aminoethanol derivative as a cathode buffer layer

Cathode buffer layer (CBL) introduced between the active layer and cathode is crucial for selectively transporting electrons and blocking holes for polymer solar cells (PSCs). Calcium (Ca) is the most commonly used CBL in conventional-structure bulk heterojunction (BHJ) PSC devices, but is prone to oxidation due to its high reactivity, inhibiting its practical applications. Herein, we applied an alcohol-soluble fullerene aminoethanol derivative (C₆₀-ETA) as an efficient CBL surpassing Ca in conventional-structure BHJ-PSC devices, leading to obvious efficiency enhancement with the best power conversion efficiency (PCE) reaching 9.66%. C₆₀-ETA CBL was applied in PSC devices based on three different photoactive layer systems, including poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b′]dithiophene-co-3-fluorothieno[3,4-b]thiophene-2-carboxylate]:[6,6]-phenyl C₇₁-butyric acid methyl ester (PTB7-Th:PC₇₁BM), polythieno[3,4-b]thiophene-co-benzodithiophene (PTB7):PC₇₁BM and poly(4,8-bis-alkyloxybenzo(l,2-b:4,5-b′)dithiophene-2,6-diylalt-(alkylthieno(3,4-b)thiophene-2-carboxylate)-2,6-diyl) (PBDTTT-C):PC₇₁BM, affording the best PCE of 9.66%, 8.51% and 7.19%, respectively, which are all higher than those of the corresponding devices based on the commonly used Ca CBL. The mechanism of efficiency enhancement of C₆₀-ETA CBL relative to Ca is studied, revealing that C₆₀-ETA CBL may induce improvements on both the interfacial contact between the active layer/cathode and electron transport, facilitating electron extraction by the Al cathode, and consequently leading to the increase of short-circuit current density (J_sc), which contributes primarily to the PCE improvement.     

High‐Yield Synthesis and Electrochemical and Photovoltaic Properties of Indene‐C70 Bisadduct

[6, 6]‐Phenyl‐C₆₁‐butyric acid methyl ester (PC₆₀BM) is the widely used acceptor material in polymer solar cells (PSCs). Nevertheless, the low LUMO energy level and weak absorption in visible region are its two weak points. For enhancing the solar light harvest, the soluble C₇₀ derivative PC₇₀BM has been used as acceptor instead of PC₆₀BM in high efficiency PSCs in recent years. But, the LUMO level of PC₇₀BM is the same as that of PC₆₀BM, which is too low for the PSCs based on the polymer donors with higher HOMO level, such as poly (3‐hexylthiophene) (P3HT). Here, a new soluble C₇₀ derivative, indene‐C₇₀ bisadduct (IC₇₀BA), is synthesized with high yield of 58% by a one‐pot reaction of indene and C₇₀ at 180 °C for 72 h. The electrochemical properties and electronic energy levels of the fullerene derivatives are measured by cyclic voltammetry. The LUMO energy level of IC₇₀BA is 0.19 eV higher than that of PC₇₀BM. The PSC based on P3HT with IC₇₀BA as acceptor shows a higher V_oc of 0.84 V and higher power conversion efficiency (PCE) of 5.64%, while the PSC based on P3HT/PC₆₀BM and P3HT/PC₇₀BM displays V_oc of 0.59 V and 0.58 V, and PCE of 3.55% and 3.96%, respectively, under the illumination of AM1.5G, 100 mW cm^?2. The results indicate that IC₇₀BA is an excellent acceptor for the P3HT‐based PSCs and could be a promising new acceptor instead of PC₇₀BM for the high performance PSCs based on narrow bandgap conjugated polymer donor.     

Impact of the Nature of the Side‐Chains on the Polymer‐Fullerene Packing in the Mixed Regions of Bulk Heterojunction Solar Cells

Polymer‐fullerene packing in mixed regions of a bulk heterojunction solar cell is expected to play a major role in exciton‐dissociation, charge‐separation, and charge‐recombination processes. Here, molecular dynamics simulations are combined with density functional theory calculations to examine the impact of nature and location of polymer side‐chains on the polymer‐fullerene packing in mixed regions. The focus is on poly‐benzo[1,2‐b:4,5‐b′]dithiophene‐thieno[3,4‐c]pyrrole‐4,6‐dione (PBDTTPD) as electron‐donating material and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) as electron‐accepting material. Three polymer side‐chain patterns are considered: i) linear side‐chains on both benzodithiophene (BDT) and thienopyrroledione (TPD) moieties; ii) two linear side‐chains on BDT and a branched side‐chain on TPD; and iii) two branched side‐chains on BDT and a linear side‐chain on TPD. Increasing the number of branched side‐chains is found to decrease the polymer packing density and thereby to enhance PBDTTPD–PC₆₁ BM mixing. The nature and location of side‐chains are found to play a determining role in the probability of finding PC₆₁BM molecules close to either BDT or TPD. The electronic couplings relevant for the exciton‐dissociation and charge‐recombination processes are also evaluated. Overall, the findings are consistent with the experimental evolution of the PBDTTPD–PC₆₁BM solar‐cell performance as a function of side‐chain patterns.     

Solution Processable Fluorenyl Hexa‐peri‐hexabenzocoronenes in Organic Field‐Effect Transistors and Solar Cells

The organization of organic semiconductor molecules in the active layer of organic electronic devices has important consequences to overall device performance. This is due to the fact that molecular organization directly affects charge carrier mobility of the material. Organic field‐effect transistor (OFET) performance is driven by high charge carrier mobility while bulk heterojunction (BHJ) solar cells require balanced hole and electron transport. By investigating the properties and device performance of three structural variations of the fluorenyl hexa‐peri‐hexabenzocoronene (FHBC) material, the importance of molecular organization to device performance was highlighted. It is clear from ¹H NMR and 2D wide‐angle X‐ray scattering (2D WAXS) experiments that the sterically demanding 9,9‐dioctylfluorene groups are preventing π–π intermolecular contact in the hexakis‐substituted FHBC 4 . For bis‐substituted FHBC compounds 5 and 6 , π–π intermolecular contact was observed in solution and hexagonal columnar ordering was observed in solid state. Furthermore, in atomic force microscopy (AFM) experiments, nanoscale phase separation was observed in thin films of FHBC and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) blends. The differences in molecular and bulk structural features were found to correlate with OFET and BHJ solar cell performance. Poor OFET and BHJ solar cells devices were obtained for FHBC compound 4 while compounds 5 and 6 gave excellent devices. In particular, the field‐effect mobility of FHBC 6 , deposited by spin‐casting, reached 2.8 × 10^?3 cm² V^?1 s and a power conversion efficiency of 1.5% was recorded for the BHJ solar cell containing FHBC 6 and PC₆₁BM.     

A Cross‐Linkable Donor Polymer as the Underlying Layer to Tune the Active Layer Morphology of Polymer Solar Cells

For polymer solar cells (PSCs) with conventional configuration, the vertical composition profile of donor:acceptor in active layer is detrimental for charge carrier transporting/collection and leads to decreased device performance. A cross‐linkable donor polymer as the underlying morphology‐inducing layer (MIL) to tune the vertical composition distribution of donor:acceptor in the active layer for improved PSC device performance is reported. With poly(thieno[3,4‐b]‐thiophene/benzodithiophene):[6,6]‐phenyl C₇₁‐butyric acid methyl ester (PTB7:PC₇₁BM) as the active layer, the MIL material, PTB7‐TV , is developed by attaching cross‐linkable vinyl groups to the side chain of PTB7. PSC device with PTB7‐TV layer exhibits a power conversion efficiency (PCE) of 8.55% and short‐circuit current density (J_SC) of 15.75 mA cm^?2, in comparison to PCE of 7.41% and J_SC of 13.73 mA cm^?2 of the controlled device. The enhanced device performance is ascribed to the much improved vertical composition profile and reduced phase separation domain size in the active layer. These results demonstrate that cross‐linked MIL is an effective strategy to improve photovoltaic performance of conventional PSC devices.     

An Amidine‐Type n‐Dopant for Solution‐Processed Field‐Effect Transistors and Perovskite Solar Cells

This study reports an effective amidine‐type n‐dopant of 1,8‐Diazabicyclo[5.4.0]undec‐7‐ene (DBU) that can universally dope electron acceptors, including PC₆₁BM, N2200, and ITIC, by mixing the dopant with the acceptors in organic solvents or exposing the acceptor films in the dopant vapor. The doping mechanism is due to its strong electron‐donating property that is also confirmed via the chemical reduction of PEDOT:PSS (yielding color change). The DBU doping considerably increases the electrical conductivity and shifts the Fermi levels up of the PC₆₁BM films. When the DBU‐doped PC₆₁BM is used as an electron‐transporting layer in perovskite solar cells, the n‐doping removes the “S‐shape” of J–V characteristics, which leads to the fill factor enhancement from 0.54 to 0.76. Furthermore, the DBU doping can effectively lower the threshold voltage and enhance the electron mobility of PC₆₁BM‐based n‐channel field‐effect transistors. These results show that the DBU can be a promising n‐dopant for solution‐processed electronics.     

The Novel Additive 1‐Naphthalenethiol Opens a New Processing Route to Efficiency‐Enhanced Polymer Solar Cells

Polymer solar cells (PSCs) based on fullerene derivatives often require additives to optimize active layer morphology. Here, the novel additive 1‐naphthalenethiol (SH‐na) is proposed for processing the PSC active layer of PTB7:PC₇₁BM. Spin‐casting with SH‐na as additive achieves a power conversion efficiency (PCE) of 7.3%, compared to 6.7% for preparations containing the conventional 1,8‐diiodooctane additive. Dipping of the active layer into a methanol solution of critical SH‐na concentration increases the PCE further to 8.75%. This is mainly due to an improved open‐circuit voltage (from 0.72 to 0.79 V) together with a high achieved fill factor of 0.70. The improved PCE is correlated to the morphology optimization according to measurements of grazing incidence small/wide‐angle X‐ray scattering, neutron reflectivity, atomic force microscopy, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. The integrated results suggest that the halogen‐free additive SH‐na can form hydrogen bonds with both PTB7 and PC₇₁BM, resulting in substantially improved PTB7 crystallization and multi‐length‐scale PC₇₁BM dispersion for appropriate aggregation and networks. The subsequent dipping treatment with SH‐na further modifies the active layer morphology for a more PC₇₁BM‐enriched surface and better PC₇₁BM networks in the bulk film for an optimized electron‐to‐hole mobility ratio of 2.04, hence resulting in improved device performance.     

High‐Performance Inverted Polymer Solar Cells: Device Characterization,Optical Modeling,and Hole‐Transporting Modifications

Although high power conversion efficiencies (PCE) have already been demonstrated in conventional structure polymer solar cells (PSCs), the development of high performance inverted structure polymer solar cells is still lagging behind despite their demonstrated superior stability and feasibility for roll‐to‐roll processing. To address this challenge, a detailed study of solution‐processed, inverted‐structure PSCs based on the blends of a low bandgap polymer, poly(indacenodithiophene‐co‐phananthrene‐quinoxaline) (PIDT‐PhanQ) and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as the bulk heterojunction (BHJ) layer is carried out. Comprehensive characterization and optical modeling of the resulting devices is performed to understand the effect of device geometry on photovoltaic performance. Excellent device performance can be achieved by optimizing the optical field distribution and spatial profiles of excitons generation within the active layer in different device configurations. In the inverted structure, because the peak of the excitons generation is located farther away from the electron‐collecting electrode, a higher blending ratio of fullerene is required to provide higher electron mobility in the BHJ for achieving good device performance.