Impact of Nonfullerene Molecular Architecture on Charge Generation,Transport, and Morphology in PTB7‐Th‐Based Organic Solar Cells

Despite the rapid development of nonfullerene acceptors (NFAs), the fundamental understanding on the relationship between NFA molecular architecture, morphology, and device performance is still lacking. Herein, poly[[4,8‐bis[5‐(2‐ethylhexyl)thiophene‐2‐yl]benzo[1,2‐b:4,5‐b0]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]‐thieno[3,4‐b]thiophenediyl]] (PTB7‐Th) is used as the donor polymer to compare an NFA with a 3D architecture (SF‐PDI4) to a well‐studied NFA with a linear acceptor–donor–acceptor (A–D–A) architecture (ITIC). The data suggest that the NFA ITIC with a linear molecular structure shows a better device performance due to an increase in short‐circuit current ( J_sc) and fill factor (FF) compared to the 3D SF‐PDI4. The charge generation dynamics measured by femtosecond transient absorption spectroscopy (TAS) reveals that the exciton dissociation process in the PTB7‐Th:ITIC films is highly efficient. In addition, the PTB7‐Th:ITIC blend shows a higher electron mobility and lower energetic disorder compared to the PTB7‐Th:SF‐PDI4 blend, leading to higher values of J_sc and FF. The compositional sensitive resonant soft X‐ray scattering (R‐SoXS) results indicate that ITIC molecules form more pure domains with reduced domain spacing, resulting in more efficient charge transport compared with the SF‐PDI4 blend. It is proposed that both the molecular structure and the corresponding morphology of ITIC play a vital role for the good solar cell device performance.     

Influence of Molecular Geometry of Perylene Diimide Dimers and Polymers on Bulk Heterojunction Morphology Toward High‐Performance Nonfullerene Polymer Solar Cells

In this study, we investigate the influence of molecular geometry of the donor polymers and the perylene diimide dimers (di‐PDIs) on the bulk heterojunction (BHJ) morphology in the nonfullerene polymer solar cells (PSCs). The results reveal that the pseudo 2D conjugated 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) has better miscibility with both bay‐linked di‐PDI (B‐di‐PDI) and hydrazine‐linked di‐PDI (H‐di‐PDI) compared to its 1D analog, 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), to facilitate more efficient exciton dissociation in the BHJ films. However, the face‐on oriented π–π stacking of PTB7‐Th is severely disrupted by the B‐di‐PDI due to its more flexible structure. On the contrary, the face‐on oriented π–π stacking is only slightly disrupted by the H‐di‐PDI, which has a more rigid structure to provide suitable percolation pathways for charge transport. As a result, a very high power conversion efficiency (PCE) of 6.41% is achieved in the PTB7‐Th:H‐di‐PDI derived device. This study shows that it is critical to pair suitable polymer donor and di‐PDI‐based acceptor to obtain proper BHJ morphology for achieving high PCE in the nonfullerene PSCs.     

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.     

Structure Tuning of Crown Ether Grafted Conjugated Polymers as the Electron Transport Layer in Bulk‐Heterojunction Polymer Solar Cells for High Performance

A series of novel electron transport (ET) polymers composed of different conjugated main chains (fluorene, thiophene, and 2,7‐carbazole) and crown ether side chain (crown ether, aza‐crown ether and amine) is presented for bulk‐heterojunction polymer solar cells with poly(3‐hexylthiophene) (P3HT) or 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) as the active polymer and aluminum metal as the cathode. Unexpectedly, it is found that the main chain of ET polymers has a greater effect on the interfacial dipole than the side chain, even when attaching a high polarity group. The electron‐rich bridge atom of the main chain may also contribute appreciably to the interfacial dipole. When used as the ET layer, all of these polymers can generate an optical interference effect for redistribution of the optical electric field as an optical spacer and, therefore, allow more light to be absorbed by the active layer, thus leading to an increase in short‐circuit current density. They can also block hole diffusion to the cathode and prevent electron–hole recombination during the ET process. Among the five ET polymers investigated, PCCn6 is the most effective one, providing a remarkable improvement in the power conversion efficiency (measured in air) of the device to 8.13% compared to 5.20% for PTB7:[6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM).     

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.     

Nongeminate and Geminate Recombination in PTB7:PCBM Solar Cells

A combination of transient photovoltage (TPV), voltage dependent charge extraction (CE), and time delayed collection field (TDCF) measurements is applied to 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):[6,6]‐phenyl‐C71‐butyric acid (PC₇₁BM) bulk heterojunction solar cells to analyze the limitations of photovoltaic performance. Devices are processed from pure chlorobenzene (CB) solution and a subset is optimized with 1,8‐diiodooctane (DIO) as co‐solvent. The dramatic changes in device performance are discussed with respect to the dominating loss processes. While in the devices processed from CB solution severe geminate and nongeminate recombination is observed, the use of DIO facilitates efficient polaron pair dissociation and minimizes geminate recombination. Thus, from the determined charge carrier decay rate under open circuit conditions and the voltage dependent charge carrier densities n(V), the nongeminate loss current J_loss of the samples with DIO alone enables the reconstruction of the current/voltage (j/V) characteristics across the whole operational voltage range. Geminate and nongeminate losses are considered to describe the j/V response of cells prepared without additive, but lead to a clearly overestimated device performance. The deviation between measured and reconstructed j/V characteristics is attributed to trapped charges in isolated domains of pure fullerene phases.     

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.     

Effect of annealing-induced oxidation of molybdenum oxide on organic photovoltaic device performance

Molybdenum oxide (MoO_x) has been widely used as a hole transport layer in organic photovoltaic cells (OPVs), whose performance can be improved by inserting a MoO_x layer between an organic active layer and a transparent anode because of efficient carrier dissociation. In this study, the influence of thermally annealed MoO_x on the photovoltaic performance of OPVs was first investigated using low-bandgap polymer and [6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM) blend films as the active layer. We used three low-bandgap polymers: poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7(2,1,3-benzothiadiazole)] (PCPDTBT), poly(4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl) (PTB7), and 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) (PTB7-Th). Power conversion efficiencies were drastically increased for all investigated polymers when the as-deposited MoO_x layer was annealed at 160 °C for 5 min. In particular, a high efficiency of 6.57% was achieved when PTB7 was used; for comparison, the efficiency of a reference device with an as-deposited MoO_x layer (not subjected to annealing) was 1.40%. Specifically, the short-circuit current density and fill factor were remarkably improved after annealing, which means that efficient carrier dissociation was achieved in the active layer. We evaluated optical absorption and surface morphology to elucidate reasons behind the improved photovoltaic performance, and these parameters only slightly changed after annealing. In contrast, angle-dependent X-ray photoelectron spectroscopy revealed that the MoO_x layer was oxidized after annealing. In general, the oxygen vacancies of MoO_x act as carrier traps; a reduction in the number of carrier traps causes high hole mobility in the organic layer, which, in turn, results in an improved photovoltaic performance. Therefore, our results indicate that the annealing-induced oxidation of MoO_x is useful for achieving high photovoltaic performance.     

An Electron Acceptor with Broad Visible–NIR Absorption and Unique Solid State Packing for As‐Cast High Performance Binary Organic Solar Cells

A novel acceptor–donor–acceptor (A–D–A) type electron acceptor 6TIC‐4F with terthieno[3,2‐b]thiophene (6T) as the core unit is rationally designed and synthesized, which exhibits an extraordinarily narrow bandgap (≈1.24 eV) and strong absorption between 650 and 1000 nm. X‐ray crystallographic analysis reveals that it has unique intermolecular π–π stacking. The solar cells based on the as‐cast poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene))‐alt‐(5,5‐(1′,3′‐di‐2‐thienyl‐5′,7′‐bis(2‐ethylhexyl)benzo[1′,2′‐c:4′,5′‐c′]dithiophene‐4,8‐dione))]) (PBDB‐T): 6TIC‐4F binary blends exhibit an excellent power conversion efficiency (PCE) of 11.14% with a high J_SC of 23.00 mA cm^?2, and a high fill factor of 0.67, which represents one of the best PCE values for low bandgap (E_g < 1.3 eV)–based organic solar cells.     

Hydrogen Bond Induced Green Solvent Processed High Performance Ternary Organic Solar Cells with Good Tolerance on Film Thickness and Blend Ratios

For comprehensive development of organic solar cells (OSCs), some factors such as environmental stability, low cost, insensitive film thickness, component contents tolerance, and green preparation processes are equally crucial to achieve high power conversion efficiencies (PCEs). In this work, a small molecule 3‐(diethylamino)‐7‐imino‐7H‐benzo[4,5]imidazo[1,2‐a]chromeno[3,2‐c]pyridine‐6‐carbonitrile (DIBC), which is commercially available at low cost, is utilized to realize high‐performance ternary OSCs. Demonstrated via Fourier transform infrared and 2D‐¹HNMR, DIBC can form hydrogen bond interactions with [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) in solid films. Further electrostatic potential (ESP) calculations indicate that the hydrogen bond interaction enhances the ESP of PC₇₁BM and accelerates charge transport between donor and acceptor. As a result, poly(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b;4,5‐b0]dithiophene‐2,6‐diylalt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐)‐2‐carboxylate‐2‐6‐diyl (PTB7‐Th):DIBC:PC₇₁BM‐based ternary OSC achieves a maximum efficiency of 12.17%, which is the best result of green solvent processed fullerene OSCs at present. It is noteworthy that the ternary OSCs also show great tolerance to film thickness and blend ratios. These unique properties are attributed to the hydrogen‐bond‐linked DIBC and PC₇₁BM, which modulates molecule distribution and improves film morphology with an interpenetrating network structure. Furthermore, the DIBC containing device also exhibits good thermal and light radiation stability. These results illustrate that intermolecular hydrogen bond interaction has great potential for realizing high‐performance OSCs.     

Incorporating Graphitic Carbon Nitride (g‐C3N4) Quantum Dots into Bulk‐Heterojunction Polymer Solar Cells Leads to Efficiency Enhancement

Graphitic carbon nitride (g‐C₃N₄) has been commonly used as photocatalyst with promising applications in visible‐light photocatalytic water‐splitting. Rare studies are reported in applying g‐C₃N₄ in polymer solar cells. Here g‐C₃N₄ is applied in bulk heterojunction (BHJ) polymer solar cells (PSCs) for the first time by doping solution‐processable g‐C₃N₄ quantum dots (C₃N₄ QDs) in the active layer, leading to a dramatic efficiency enhancement. Upon C₃N₄ QDs doping, power conversion efficiencies (PCEs) of the inverted BHJ‐PSC devices based on different active layers including poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C61‐butyric acid methyl ester (P3HT:PC₆₁BM), poly(4,8‐bis‐alkyloxybenzo(l,2‐b:4,5‐b′)dithiophene‐2,6‐diylalt‐(alkyl thieno(3,4‐b)thiophene‐2‐carboxylate)‐2,6‐diyl):[6,6]‐phenyl C₇₁‐butyric acid methyl ester (PBDTTT‐C:PC₇₁BM), and 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] (PTB7‐Th):PC₇₁BM reach 4.23%, 6.36%, and 9.18%, which are enhanced by ≈17.5%, 11.6%, and 11.8%, respectively, compared to that of the reference (undoped) devices. The PCE enhancement of the C₃N₄ QDs doped BHJ‐PSC device is found to be primarily attributed to the increase of short‐circuit current (J_sc), and this is confirmed by external quantum efficiency (EQE) measurements. The effects of C₃N₄ QDs on the surface morphology, optical absorption and photoluminescence (PL) properties of the active layer film as well as the charge transport property of the device are investigated, revealing that the efficiency enhancement of the BHJ‐PSC devices upon C₃N₄ QDs doping is due to the conjunct effects including the improved interfacial contact between the active layer and the hole transport layer due to the increase of the roughness of the active layer film, the facilitated photoinduced electron transfer from the conducting polymer donor to fullerene acceptor, the improved conductivity of the active layer, and the improved charge (hole and electron) transport.     

Influence of the Electron Deficient Co‐Monomer on the Optoelectronic Properties and Photovoltaic Performance of Dithienogermole‐based Co‐Polymers

A series of donor–acceptor (D–A) conjugated polymers utilizing 4,4‐bis(2‐ethylhexyl)‐4H‐germolo[3,2‐b:4,5‐b′]dithiophene ( DTG ) as the electron rich unit and three electron withdrawing units of varying strength, namely 2‐octyl‐2H‐benzo[d][1,2,3]triazole ( BTz ), 5,6‐difluorobenzo[c][1,2,5]thiadiazole ( DFBT ) and [1,2,5]thiadiazolo[3,4‐c]pyridine ( PT ) are reported. It is demonstrated how the choice of the acceptor unit ( BTz , DFBT , PT ) influences the relative positions of the energy levels, the intramolecular transition energy (ICT), the optical band gap (E_g^opt), and the structural conformation of the DTG ‐based co‐polymers. Moreover, the photovoltaic performance of poly[(4,4‐bis(2‐ethylhexyl)‐4H‐germolo[3,2‐b:4,5‐b′]dithiophen‐2‐yl)‐([1,2,5]thiadiazolo[3,4‐c]pyridine)] ( PDTG‐PT ), poly[(4,4‐bis(2‐ethylhexyl)‐4H‐germolo[3,2‐b:4,5‐b′]dithiophen‐2‐yl)‐(2‐octyl‐2H‐benzo[d][1,2,3]triazole)] ( PDTG‐BTz ), and poly[(4,4‐bis(2‐ethylhexyl)‐4H‐germolo[3,2‐b:4,5‐b′]dithiophen‐2‐yl)‐(5,6‐difluorobenzo[c][1,2,5]thiadiazole)] ( PDTG‐DFBT ) is studied in blends with [6,6]‐phenyl‐C₇₀‐butyric acid methyl ester ( PC₇₀BM ). The highest power conversion efficiency (PCE) is obtained by PDTG‐PT (5.2%) in normal architecture. The PCE of PDTG‐PT is further improved to 6.6% when the device architecture is modified from normal to inverted. Therefore, PDTG‐PT is an ideal candidate for application in tandem solar cells configuration due to its high efficiency at very low band gaps (E_g^opt = 1.32 eV). Finally, the 6.6% PCE is the highest reported for all the co‐polymers containing bridged bithiophenes with 5‐member fused rings in the central core and possessing an E_g^opt below 1.4 eV.     

Effect of Palladium-Tetrakis(Triphenylphosphine) Catalyst Traces on Charge Recombination and Extraction in Non-Fullerene-based Organic Solar Cells

The effect of the cross-coupling catalyst tetrakis(triphenylphosphine)palladium(0) (Pd(PPh₃)₄) on the performance of a model organic bulk-heterojunction solar cell composed of a blend of 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}) (PTB7-Th) donor and 3,9-bis(2-methylene-((3-(1,1-dicyanomethylene)-6,7-difluoro)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene (IOTIC-4F) non-fullerene acceptor is investigated. The effect of intentional addition of different amounts of Pd(PPh₃)₄ on morphology, free charge carrier generation, non-geminate bulk trap- and surface trap-assisted recombination as well as bimolecular recombination and charge extraction is quantified. This work shows that free charge carrier generation is affected significantly, while the impact of Pd(PPh₃)₄ on non-geminate recombination processes is limited because the catalyst does not facilitate efficient trap-assisted recombination. The studied system shows substantial robustness towards the addition of Pd(PPh₃)₄ in small amounts.     

Tuning the Charge Carrier Polarity of Organic Transistors by Varying the Electron Affinity of the Flanked Units in Diketopyrrolopyrrole‐Based Copolymers

Fine‐tuning of the charge carrier polarity in organic transistors is an important step toward high‐performance organic complementary circuits and related devices. Here, three new semiconducting polymers, namely, pDPF‐DTF2, pDPSe‐DTF2, and pDPPy‐DTF2, are designed and synthesized using furan, selenophene, and pyridine flanking group‐based diketopyrrolopyrrole cores, respectively. Upon evaluating their electrical properties in transistor devices, the best performance has been achieved for pDPSe‐DTF2 with the highest and average hole mobility of 1.51 and 1.22 cm² V^?1 s^?1, respectively. Most intriguingly, a clear charge‐carrier‐polarity change is observed when the devices are measured under vacuum. The pDPF‐DTF2 polymer exhibits a balanced ambipolar performance with the µ_h/µ_e ratio of 1.9, whereas pDPSe‐DTF2 exhibits p‐type dominated charge carrier transport properties with the µ_h/µ_e ratio of 26.7. Such a charge carrier transport change is due to the strong electron‐donating nature of the selenophene. Furthermore, pDPPy‐DTF2 with electron‐withdrawing pyridine flanking units demonstrates unipolar n‐type charge transport properties with an electron mobility as high as 0.20 cm² V^?1 s^?1. Overall, this study demonstrates a simple yet effective approach to switch the charge carrier polarity in transistors by varying the electron affinity of flanking groups of the diketopyrrolopyrrole unit.     

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.     

Wide Bandgap Molecular Acceptors with a Truxene Core for Efficient Nonfullerene Polymer Solar Cells: Linkage Position on Molecular Configuration and Photovoltaic Properties

Two wide bandgap star‐shaped small molecular acceptors, para‐TrBRCN and meta‐TrBRCN , are synthesized for efficient nonfullerene polymer solar cells (PSCs). The tiny structural variation by just changing the linkage positions affects largely the inherent properties of the resulting molecules. Both molecules have a nonplanar 3D structure, which can prevent the excessively aggregation to realize the optimized morphology and ideal domain size in their active blends. Compared to para‐TrBRCN , meta‐TrBRCN exhibits the smaller distortions between the truxene skeleton and the benzothiadiazole units, which would also lead to the enhanced π–π stacking and charge transfer. When blending with PTB7‐Th, high power conversion efficiencies (PCEs) of 10.15% and 8.28% are obtained for meta‐TrBRCN and para‐TrBRCN devices, respectively. To make up the weak absorption of above binary active blend in the longer wavelength region and increase the whole device performance further, low bandgap 3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)‐indanone)‐5,5,11,11‐tetrakis(4‐hexylthienyl)‐dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]‐dithiophene (ITIC‐Th) is added as the second acceptor material to fabricate ternary blend PSCs. After adding 20 wt% of ITIC‐Th, the resulting devices exhibit the well‐balanced optical absorption and fine‐tuned morphology, giving rise to the significantly improved PCE of 11.40% with much higher J _sc of 18.25 mA cm^?2 and fill factor of 70.2%.     

Alkoxy‐Functionalized Thienyl‐Vinylene Polymers for Field‐Effect Transistors and All‐Polymer Solar Cells

π‐conjugated polymers based on the electron‐neutral alkoxy‐functionalized thienyl‐vinylene (TVTOEt) building‐block co‐polymerized, with either BDT (benzodithiophene) or T2 (dithiophene) donor blocks, or NDI (naphthalenediimide) as an acceptor block, are synthesized and characterized. The effect of BDT and NDI substituents (alkyl vs alkoxy or linear vs branched) on the polymer performance in organic thin film transistors (OTFTs) and all‐polymer organic photovoltaic (OPV) cells is reported. Co‐monomer selection and backbone functionalization substantially modifies the polymer MO energies, thin film morphology, and charge transport properties, as indicated by electrochemistry, optical spectroscopy, X‐ray diffraction, AFM, DFT calculations, and TFT response. When polymer P7 is used as an OPV acceptor with PTB7 as a donor, the corresponding blend yields TFTs with ambipolar mobilities of μ_e = 5.1 × 10^?3 cm² V^–1 s^–1 and μ_h = 3.9 × 10^?3 cm² V^–1 s^–1 in ambient, among the highest mobilities reported to date for all‐polymer bulk heterojunction TFTs, and all‐polymer solar cells with a power conversion efficiency (PCE) of 1.70%, the highest reported PCE to date for an NDI‐polymer acceptor system. The stable transport characteristics in ambient and promising solar cell performance make NDI‐type materials promising acceptors for all‐polymer solar cell applications.     

Alkylsilyl Functionalized Copolymer Donor for Annealing‐Free High Performance Solar Cells with over 11% Efficiency: Crystallinity Induced Small Driving Force

The contradiction between enlarging the offset between energy levels of donor/acceptor and the required driving force for exciton split leads to a trade‐off between open circuit voltage (V_OC) and short circuit current density (J_SC), which is a big challenge for development of high performance polymer solar cells (PSCs). Some advanced works reported the PSCs with low photon energy loss (E_loss) and small driving force, but the correlation of molecular structures of light‐harvesting system and driving force is still unclear. In this work, a new alkylsilyl functionalized copolymer donor PBDS‐T (PBDST: poly[(2,6trialkylsilyl thiophen2yl)benzo[1,2b:4,5b′]dithiophene))alt(5,5(1′,3′di2thienyl5′,7′bis(2ethylhexyl)benzo[1′,2′c:4′,5′c′]dithiophene4,8dione))]) with low‐lying energy levels was designed for efficient PSCs. By monitoring the Photoluminescence quenching of the bulk and bilayer heterojunctions, small driving forces, ?E_HOMO of 0.15 eV and ?E_LUMO of 0.22 eV were founded to allow for efficient charge transfer, which were observed to correlate with the crystalline PBDS‐T and the optimal morphology in PBDS‐T:ITIC (ITIC: 3,9bis(2methylene(3(1,1dicyanomethylene)indanone))5,5,11,11tetrakis(4hexylphenyl)dithieno[2,3d:2′,3′d′]sindaceno[1,2b:5,6b′]dithiophene). Simultaneously improved V_OC, J_SC and small Eloss boosted the PCE over 11%, which is one of the highest values for annealing‐free device. These results shield a light on precise design of a light‐harvesting system with small driving force to simultaneously improve the V_OC and J_SC for highly efficient PSCs.     

An insight on oxide interlayer in organic solar cells: From light absorption and charge collection perspectives

A comprehensive study of the effect of oxide interlayer on the performance of bulk-heterojunction organic solar cells (OSCs), based on 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): [6,6]-phenyl C71 butyric acid methyl ester (PC₇₀BM) blend system, is carried out by optical simulation, interfacial exciton dissociation and charge collection analyses. It is found that a PTB7:PC₇₀BM blend layer thickness optimized for maximum light absorption in OSCs does not generally give rise to the highest power conversion efficiency (PCE). OSCs, e.g., based on PTB7:PC₇₀BM blend system, can benefit from the oxide interlayer in two ways, (1) to enhance the built-in potential for reducing recombination loss of the photo-generated charges, and (2) to improve charge collection by removal of unfavorable interfacial exciton dissociation. The combined effects result in ∼20% improvement in PCE over an optimized control cell, having an identical layer configuration without an oxide interlayer.     

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.